TW201111345A - Organic ambipolar light emitting materials - Google Patents
Organic ambipolar light emitting materials Download PDFInfo
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- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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Abstract
Description
201111345 六、發明說明: 【發明所屬之技術領域】 本發明概言之係關於發光有機材料、尤其電致發光有機 材料,且係關於含有該等化合物之發光裝置。 【先前技術】 某些有機材料因在分子中包括π鍵延伸系統而能夠傳導 電何。即,具有相連或共軛π系統之化合物(例如聚伸芳基 化合物或聚伸芳基伸乙烯基化合物(例如聚(伸苯基伸乙烯 基)及聚荞))具有重疊並沿該分子延伸之一系列π分子轨 道。當向分子施加電壓時,此等延伸π分子軌道在未充滿 時或僅料地充滿電子時可為額夕卜電子沿該分子之傳輸提 供「通道」。可跨越導電有機材料形成若干該等延伸兀軌 道’其每一者皆具有不同結構及能級。具有最低能級之分 子軌道通常係用於傳輸由電極提供之電子的有效路徑。 為使此等材料(且具體而言聚合物)在跨越分子傳輸電子 時發光,-或多個電子必須自充滿或部分充滿之較高能量 執道移動至未充滿或部分充滿之較低能量軌道。若電子在 自问忐態傳遞至低能態時所釋放出之能量在可見光譜中, 則此等分子將發射光。 簡σ之 ^將電/同注入導電有機分子中時,該分子變為 帶正電% ,且反之當將電子注入此—分子中時,其變為帶 負電荷。帶電荷分子可自田比鄰分子獲得相反電荷,從而在 合有該導電有機分子之組合物中引起電荷傳輸。注入電子 及電洞可在發射層内重新結合,形成結合電子/電洞對(稱 149615.doc 201111345 為激發子)’當其自激發態鬆弛至較低能態時可發射能 量。視所發射能量之波長而定,能量可以紫外光或可見光 形式釋放。 電致發光有機材料可為共軛聚合物或有機小分子。聚合 電致發光有機材料之實例包括聚(Μ-伸苯基伸乙烯基)、 聚苐、及其衍生物。電致發光聚合物因其溶液可處理性而 八有及引力’故係製造含有電致發光有機材料之電子裝置 相對具有成本效益之方法。然而,因聚合材料可能在聚 合物骨架中含有一定量的結構缺陷、於聚合期間產生之副 產物、及留在聚·合物鏈上之末端基團,故聚合發光材料可 月匕難以達成高純度。在聚合物中存在此等雜質/缺陷將顯 著影響裝置效率及壽命。 非聚合有機小分子代表另一類發光材料。小分子之極高 义可藉Μ昇華《重結晶製程達成,&較發《聚合物有 子已作為發射體或作為電荷傳輸材料廣泛地用於 OLED裝置中。然而,小分子通常係藉助真空沈積進行處 理’故不具有成本效益。此一製程對於大量生產係不合意 的。為克服聚合發光材料純度差及小分子高成本處理之缺 點’需要研發出可藉助溶液製程處理之新發光材料。 聚口材料及非聚合材料二者均已用於有機發光裝置(例 如有機發光二極體(OLED))中。 热阳,冨前許多有機201111345 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates generally to luminescent organic materials, particularly electroluminescent organic materials, and to luminescent devices containing such compounds. [Prior Art] Certain organic materials are capable of conducting electricity by including a π bond extension system in the molecule. That is, a compound having a contiguous or conjugated π system (for example, a poly(arylene) compound or a poly(arylene-extended vinyl compound) (for example, poly(phenylene vinyl) and polyfluorene) has an overlap and one of the extensions along the molecule Series π molecular orbitals. When a voltage is applied to a molecule, the extended π molecular orbitals provide a "channel" for the transmission of the electrons along the molecule when they are not full or when only the electrons are filled. A plurality of the elongated track tracks can be formed across the conductive organic material, each of which has a different structure and energy level. The molecular orbit with the lowest energy level is typically used to transmit the effective path of the electrons provided by the electrodes. In order for such materials (and in particular polymers) to emit light when electrons are transported across molecules, - or multiple electrons must move from a higher energy or partially filled higher energy orbit to a lower energy or partially filled lower energy orbit. . If the electrons are released in the visible spectrum when the electrons are transferred to the low energy state, then the molecules will emit light. When sigma is injected into the conductive organic molecule, the molecule becomes positively charged, and conversely when electrons are injected into the molecule, it becomes negatively charged. The charged molecule can obtain an opposite charge from the field adjacent molecule, thereby causing charge transport in the composition incorporating the conductive organic molecule. The injected electrons and holes can be recombined in the emissive layer to form a combined electron/hole pair (excited by 149615.doc 201111345), which emits energy when it relaxes from the excited state to the lower energy state. Depending on the wavelength of the emitted energy, the energy can be released in the form of ultraviolet light or visible light. The electroluminescent organic material can be a conjugated polymer or an organic small molecule. Examples of the polymerizable electroluminescent organic material include poly(fluorene-phenylene vinyl), polyfluorene, and derivatives thereof. Electroluminescent polymers are relatively cost-effective in the manufacture of electronic devices containing electroluminescent organic materials because of their solution handleability. However, since the polymeric material may contain a certain amount of structural defects in the polymer skeleton, by-products generated during the polymerization, and terminal groups remaining on the polymer chain, the polymeric luminescent material may be difficult to achieve at a high temperature. purity. The presence of such impurities/defects in the polymer will significantly affect device efficiency and lifetime. Non-polymeric organic small molecules represent another class of luminescent materials. The extremely high level of small molecules can be achieved by the sublimation of the "recrystallization process," and the "polymers have been widely used as emitters or as charge transport materials in OLED devices. However, small molecules are usually treated by vacuum deposition' and are therefore not cost effective. This process is not desirable for mass production systems. In order to overcome the shortcomings of poor purity of polymeric luminescent materials and high cost of small molecules, it is necessary to develop new luminescent materials that can be processed by solution processes. Both the land material and the non-polymer material have been used in organic light-emitting devices such as organic light-emitting diodes (OLEDs). Hot Yang, many organic before
、 奴兀何科逋吊具有个于撰r .¾何I 特性。通常’發光材料僅能僂 1里此得導種電荷載流子(電订 電子),但通常不能同時傳導-者 了埒等一者。舉例而言,聚(1,4 149615.doc 201111345 苯基伸乙職)或經烧氧基取代之聚(1,4伸笨基伸乙稀基) 係良好之電/同傳輸體,而參_(8_羥基喹琳)鋁(m)(Alq3)係 電子傳輸體。OLED裝置中之不平衡電荷傳輸導致低裝置 效率。 為解決此問題,已開發出具有電洞注入層、電洞傳輸 層、電子注入層及電子傳輸層中一者或多者之多層裝置。 典型構造包括電洞傳輸層、發射層及電子傳輸層,可能包 括電洞注入層及/或電子注入層。此方法可改良裝置效 率’但會增加複雜性及成本。 解决此問題之另一方法係藉由向材料中納入電洞傳輸部 分、或電子傳輸部分或該二者來調整材料之電荷傳輸性質 以試圖改良裝置性能。 儘管已研發出一些包含電洞傳輸部分及電子傳輸部分中 一者或二者之材料,且性能可能優於僅含有一種組份之材 料,但迄今基於該等材料之報導裝置性能仍不令人滿意。 原則上,當使用含有電洞傳輸部分及電子傳輸部分二者之 雙極化合物作為發射料,可簡化〇刷裝置結構並藉此 具有成本效益。然而,本發明者已觀察到雙極化合物通常 具有較大偶極矩,此將導致較強之分子内及/或分子間相 互作用。具體而言,供電子部分及拉電子部分二者共存於 刀子中將在分子中引發偶極矩。本發明者已觀察到各組份 之供電子及拉電子作用越強,則分子中偶極矩越大。另 卜L電子部分與拉電子部分越靠近,偶極矩就越大。 分子中之偶極矩通常將會引起較強之分子相互作用,尤 149615.doc 201111345 其係在固態時。眾所周知分子間相互作用將導致較低之裝 置效率’此係由於在OLED裝置中形成激發子(excjmer)/激 態複合物(exciplex)所致。另外’激發子/激態複合物發射 將使發射光譜向較長波長側移動。此會導致低裝置效率及 發射光譜之紅移。 作為OLED關鍵組份中之一者,可應用於全彩色顯示器 或固態照明中之藍色發光材料,與綠色或紅色發光材料相 比,因其相對較低之裝置效率及較短壽命,故在〇Led研 九中其係最具挑戰性之課題。舉例而言,上文所提及之雙 極化合物之不期望行為使得研發高性能深藍色發光材料極 具挑戰性。具體而言,該等雙極化合物之紅移特性對於藍 光發射係不合意的。 因此,需要可用於電致發光裝置中有機發光層中之新材 料且具體而言新藍色發光材料。 【發明内容】 本發明提供發光化合物及材料、其製備方法及其在發光 裝置(包括電致發光二極體)中之用途。 本發明係關於同時具有用於電洞傳輸之供電子部分及多 個用於電子傳輸之拉電子部分的雙極化合物。 本發明實施例對電洞及電子二者皆具有平衡電荷傳輸性 質。此外,本文所述發光材料之實施例具有受控分子偶極 矩從而可消除$減小分子内《分子間相互作肖,以達成 问效率及深藍色光發射。各實施例亦可達成較佳之藍光色 純度。 149615.doc 201111345 在其最一般之情形下,本發明提出雙極化合物包含中心 電洞傳輪核心及至少三個與該核心相連之臂,其中每一臂 皆包含電子傳輸部分及發射部分。 更具體而言,本發明係關於電致發光雙極材料,其包含 核心中供電子三級氮基團及用以提供電子傳輸魏之三個 或更多個具有缺電子基團之共輛臂;其製造方法及納入該 荨發光材料之電致發光裝置。 在一個態樣中,本發明提供化合物,其包含:(1)電洞 傳輸核心部分’該電洞傳輸核心部分包含三級氮部分;及 ⑺至少三個電子傳輸臂部分,其自該核心延伸每一電子 傳輸臂部㈣包含電子傳輪衫及發射部分。 在又樣中,本發明提供包含式I結構之化合物, 其中:The slave 兀 兀 具有 具有 has a feature of the creator. Usually, the luminescent material can only be used to conduct charge carriers (electro-depositive electrons), but it is usually not possible to conduct at the same time. For example, poly (1,4 149615.doc 201111345 phenyl extension) or alkoxy-substituted poly (1,4 extension base) is a good electrical / co-transporter, and _ ( 8_Hydroxyquinolin) Aluminum (m) (Alq3) is an electron transporter. Unbalanced charge transfer in OLED devices results in low device efficiency. To solve this problem, a multilayer device having one or more of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer has been developed. Typical configurations include a hole transport layer, an emissive layer, and an electron transport layer, possibly including a hole injection layer and/or an electron injection layer. This approach can improve device efficiency' but adds complexity and cost. Another method for solving this problem is to attempt to improve device performance by incorporating a hole transport portion, or an electron transport portion, or both into the material to adjust the charge transport properties of the material. Although materials have been developed that include one or both of the hole transport portion and the electron transport portion, and the performance may be superior to materials containing only one component, the performance of the reporting device based on such materials has not been so far satisfaction. In principle, when a bipolar compound containing both a hole transporting portion and an electron transporting portion is used as the emitter, the structure of the brushing device can be simplified and thereby cost-effective. However, the inventors have observed that bipolar compounds generally have larger dipole moments which result in stronger intramolecular and/or intermolecular interactions. Specifically, the coexistence of both the electron donating moiety and the electron withdrawing moiety in the knife will induce a dipole moment in the molecule. The inventors have observed that the stronger the electron donating and electron pulling action of each component, the greater the dipole moment in the molecule. The closer the L electron portion is to the pulled electron portion, the larger the dipole moment. The dipole moment in the molecule will usually cause stronger molecular interactions, especially in the solid state. It is well known that intermolecular interactions will result in lower device efficiencies' due to the formation of excjmer/exciplex in OLED devices. In addition, the exciton/exciplex complex emission will shift the emission spectrum toward the longer wavelength side. This can result in low device efficiency and red shift in the emission spectrum. As one of the key components of OLED, it can be applied to blue light-emitting materials in full-color displays or solid-state lighting. Compared with green or red luminescent materials, due to its relatively low device efficiency and short life, 〇Led studied the most challenging topics in the Nine. For example, the undesired behavior of the bipolar compounds mentioned above makes the development of high performance deep blue luminescent materials extremely challenging. In particular, the red shift characteristics of the bipolar compounds are undesirable for blue light emitting systems. Therefore, there is a need for new materials and, in particular, new blue luminescent materials that can be used in organic light-emitting layers in electroluminescent devices. SUMMARY OF THE INVENTION The present invention provides luminescent compounds and materials, methods for their preparation, and their use in luminescent devices, including electroluminescent diodes. The present invention relates to a bipolar compound having both an electron-donating portion for hole transport and a plurality of electron-trapping portions for electron transport. Embodiments of the present invention have balanced charge transport properties for both the hole and the electron. In addition, embodiments of the luminescent materials described herein have controlled molecular dipole moments that eliminate the need to reduce intramolecular "intermolecular interactions" to achieve efficiency and deep blue light emission. The preferred embodiment also achieves a preferred blue color purity. 149615.doc 201111345 In its most general case, the present invention proposes that the bipolar compound comprises a central hole transporting core and at least three arms connected to the core, wherein each arm comprises an electron transporting portion and an emitting portion. More particularly, the present invention relates to electroluminescent bipolar materials comprising electron-donating tertiary nitrogen groups in the core and three or more common arms having electron-deficient groups for providing electron transport. a method of manufacturing the same, and an electroluminescent device incorporating the same. In one aspect, the invention provides a compound comprising: (1) a hole transport core portion 'the hole transport core portion comprising a tertiary nitrogen portion; and (7) at least three electron transport arm portions extending from the core Each of the electron transfer arm portions (4) includes an electronic transfer shirt and a transmitting portion. In still another aspect, the invention provides a compound comprising a structure of formula I, wherein:
149615.doc 201111345 包含 核心部分 況經取代; 臂部分「B, ' Γ~Β~*Π Β ~~Ξ- ^ — L-J及L_g3 J中之每一者獨立地包含 芳基、芳基伸乙烯基或芳基伸乙块基,且 且 至少-個含有二級氮之料,其視情 視情況經取代; η、P及q中每一者獨立地為1至50 且其中 該等f部分中至少三者係、電子傳輸臂部分JL獨立地包含 發射部分及可視情況經取代之缺電子芳基、芳基伸乙烯基 或芳基伸乙炔基。 在又-態樣中,本發明提供包含式π結構之化合物:149615.doc 201111345 contains the core part of the situation; arm part "B, ' Γ ~ Β ~ * Π Β ~ ~ Ξ - ^ - each of LJ and L_g3 J independently contains aryl, aryl vinyl or An aryl group, and at least one material containing a secondary nitrogen, which is optionally substituted; η, P and q are each independently from 1 to 50 and wherein at least three of the f portions The electron transport arm portion JL independently comprises an emitting portion and optionally a substituted electron-deficient aryl group, an aryl-vinyl group or an aryl-exetylene group. In a further aspect, the invention provides a compound comprising a structure of the formula π :
I /N\ (B2)p(Ar2)b (Ar3)e(B3)q (Π) 其中:I /N\ (B2)p(Ar2)b (Ar3)e(B3)q (Π) where:
An、AO及Αι*3中之每一者獨立地為伸芳基、伸芳基伸乙 烯基、伸芳基伸乙炔基或胺基伸芳基且視情況經取代; Β〗、Β2及A中之每一者獨立地係如上文所定義; 且 a、b及c中之每一者獨立地為〇至2〇;且 η、p及q中之每一者獨立地係如上文所定義; 且其中: 至少三個選自(B,)n、(B:及(B3)q之Bx各自獨立地包含 149615.doc -8 · 201111345 發射部分及可視情況經取代之缺電子芳基、芳基伸乙烯基 或芳基伸乙快基。 在又一態樣中,本發明提供包含式III結構之化合物: [(Ar4)d(A「5)e]nEach of An, AO and Αι*3 is independently an aryl group, an extended aryl group, an aryl group or an amine group, and optionally substituted; Β, Β2 and A One is independently as defined above; and each of a, b, and c is independently 〇 to 2〇; and each of η, p, and q is independently as defined above; : at least three Bx selected from (B,)n, (B: and (B3)q each independently comprise 149615.doc -8 · 201111345 emitting moiety and optionally substituted electron-deficient aryl, aryl vinyl Or an aryl-extension group. In yet another aspect, the invention provides a compound comprising a structure of formula III: [(Ar4)d(A"5)e]n
II
[Afi]a[Afi]a
[Ar2]b [A「3】c / \ [(Ar6MAr7)g]p [(Ar8)h(Ar9),]q (HI) (HI) 其中[Ar2]b [A"3]c / \ [(Ar6MAr7)g]p [(Ar8)h(Ar9),]q (HI) (HI) where
Ar,、Ar2及Ar3係如上文所定義;且 a、b、c、n、p&q中之每一者皆係如上文所定義; 且其中Ar, Ar2 and Ar3 are as defined above; and each of a, b, c, n, p&q is as defined above;
Ar4、Ar5、Ar6、Ar7、Ar8及Αγ9中之每一者獨立地為伸 芳基、伸芳基伸乙烯基或伸芳基伸乙炔基且視情況經取 代; d、 f及h中之每一者獨立地為1至2〇;且 e、 g及i中之每一者獨立地為1至2〇 ; 且其中 選自[(Ar4)d(Ar5)e]n、[(Ar6)f(Ar7)g]p 及[(Ar8)h(Ar9)山之 Ars、Ar?及A1·9中之至少三者各自獨立地包含缺電子芳基、 芳基伸乙稀基或芳基伸乙炔基。 在又一態樣中,本發明提供式(IV)化合物: 1496l5.doc 201111345Each of Ar4, Ar5, Ar6, Ar7, Ar8, and Αγ9 is independently an aryl group, an extended aryl group, or an aryl ethynyl group, and is optionally substituted; each of d, f, and h Independently 1 to 2 〇; and each of e, g, and i is independently 1 to 2 〇; and wherein it is selected from [(Ar4)d(Ar5)e]n, [(Ar6)f(Ar7 At least three of g]p and [(Ar8)h(Ar9) mountain Ars, Ar?, and A1·9 each independently comprise an electron deficient aryl group, an aryl extended ethylene group or an aryl extended ethynyl group. In yet another aspect, the invention provides a compound of formula (IV): 1496l5.doc 201111345
Ar4a&Ar4b中之每一去 有獨立地係如上文針對Ar4所定義;Each of Ar4a&Ar4b has an independent basis as defined above for Ar4;
Ar5a& Ar5b中之每—去 有獨立地係如上文針對Ar5所定義;Each of Ar5a& Ar5b has an independent system as defined above for Ar5;
Ar6a& Ar6b中之每一去想 考獨立地係如上文針對八1"6所定義; 八〜及Aru中之每一者獨立地係如上文針對所定義; 8a& Af8b t之每_者獨立地係如上文針對仏所定義·,且 八〜及Ar9b中之每—者獨立地係如上文針對Ar9所定義; 且其中 d|及d2中之每—者獨立地係如上文針對d所定義; e〗及h中之每一者獨立地係如上文針對e所定義; fi及G中之每一者獨立地係如上文針對[所定義; &1及82中之每一者獨立地係如上文針對g所定義; hl及h2中之每—者獨立地係如上文針對h所走義;且 11及12中之每一者獨立地係如上文針對i所定義; 149615.doc 201111345 且其中 選自(Ar4a)di(Ar5a)ei、(Ar4b)d2(Ar5b)e2、(A:r6a)fl(Ar7a)gl、 (Ar6b)f2(Ar7b)g2、(Ar8a)hl(Ar9a)il&(Ar8b)h2(Ar9b)i2 之 Ar5a、Each of Ar6a&Ar6b is independently defined as defined above for VIII<6; each of VIII~ and Aru is independently defined as defined above; 8a& Af8b t is independent The hierarchy is as defined above for 仏, and each of VIII and Ar9b is independently as defined above for Ar9; and wherein each of d| and d2 is independently as defined above for d Each of e and h is independently as defined above for e; each of fi and G is independently as defined above for [as defined; & 1 and 82 independently As defined above for g; each of hl and h2 is independently as described above for h; and each of 11 and 12 is independently as defined above for i; 149615.doc 201111345 And wherein it is selected from (Ar4a)di(Ar5a)ei, (Ar4b)d2(Ar5b)e2, (A:r6a)fl(Ar7a)gl, (Ar6b)f2(Ar7b)g2, (Ar8a)hl(Ar9a)il& Ar5a of (Ar8b)h2(Ar9b)i2,
Ar5b、Ar7a、Ar7b、Ar9aA Ar9b中之至少三者各自獨立地為 缺電子芳基、芳基伸乙烯基或芳基伸乙炔基且視情況經取 代。 在又一態樣中’本發明提供式(V)化合物: (Ar4)d(Ar5)eAt least three of Ar5b, Ar7a, Ar7b, Ar9aA Ar9b are each independently an electron-deficient aryl group, an aryl-vinyl group or an aryl-exetylene group, and are optionally substituted. In still another aspect, the invention provides a compound of formula (V): (Ar4)d(Ar5)e
(V) 其中(V) where
Ar4、Ar5、Ar6、Ar7、Ar8及Ar9中之每一者獨立地係如 上文所定義; Αι^ 〇獨立地係如上文針對Αγ4所定義;Each of Ar4, Ar5, Ar6, Ar7, Ar8, and Ar9 is independently as defined above; Αι^ 〇 is independently as defined above for Αγ4;
Arn獨立地係如上文針對Αγ5所定義; d、e、f、g、h&i中之每一者獨立地係如上文所定義; j獨立地係如上文針對d所定義;且 k獨立地係如上文針對e所定義; 149615.doc -11- 201111345 且其中 選自(Ar4)d(Ar5)e 、 (Ar6)f(Ar7)g 、 (Ar8)h(Ar9)i 及 (Αη〇ΜΑΓ")^ΑΓ5、ΑΓ7、Ar9及Ari丨中之至少三者各自獨 立地為缺電子芳基、芳基伸乙稀基或芳基伸乙炔基且視情 況經取代。 在又一態樣中,本發明提供包含兩個或更多個衍生自如 本文所述化合物之單元之寡聚物或聚合物。 在又一態樣中,本發明提供包含兩個或更多個衍生自如 本文所述化合物之單元之樹枝狀聚合物。 在又一態樣中,本發明提供包含如本文所述化合物之發 光裝置。 在另一態樣中,本發明提供包含如本文所述化合物之有 機電致發光裝置。 在相關態樣中,本發明提供包含如本文所述化合物之有 機發光二極體(OLED;)。 在另一態樣中,提供包含如本文所述化合物之薄膜。 在又一態樣中,提供包含陽極、陰極及如本文所述薄膜 之裝置,s亥薄膜佈置於該陽極與該陰極之間。 在又一態樣中,提供裝置,其包含:陽極;佈置於該陽 極上之發射層,該發射層包含如本文所述化合物;及佈置 於該發射層上之陰極。 在另一態樣中,本發明提供包含發射層之裝置,其中該 發射層包含如本文所述化合物或薄膜。 在另一態樣中,提供裝置,其包含:陽極;佈置於該陽 149615.doc •12· 201111345 極上之電洞傳輸層;佈置於該電洞傳輸層上之發射層;佈 置於該發射層上之電子傳輸層;及佈置於該電子傳輸層上 之陰極;其中該電洞傳輸層、該發射層及該電子傳輸層中 之至少一者包含如本文所述化合物或薄膜。 在再一態樣中,提供裝置,其包含:陽極;佈置於該陽 極上之電洞注入層;佈置於該電洞注入層上之電洞傳輸 層,佈置於该電洞傳輸層上之發射層;佈置於該發射層上 之電子傳輸層;及佈置於該電子傳輸層上之電洞阻擋層; 佈置於該發射層上之電子注入層;佈置於該電子注入層上 之陰極;其中該電洞傳輸層、該發射層或該電子傳輸層中 之至少一者包含如本文所述化合物或薄膜。 在又態樣中,本發明提供包含作用層之光電伏打電 池,其中該作用層包含如本文所述化合物或薄膜。 在又一態樣中,本發明提供包含感測層之化學或生物感 測器其中6亥感測層包含如本文所述化合物或薄膜。 適宜地,本文所提及之裝置係顯示器裝置,例如顯示器 面板。 因此,本發明之又一態樣提供包含如本文所述化合物或 " 薄膜之顯示器裝置。 、 在又—態樣中,本發明提供製備如本文所述化合物之方 法。 在又—態樣中,本發明提供製備如本文所述裝置(例如 OLED或顯示器裝置)之方法。 在又—態樣中,本發明提供如本文所述化合物在如本文 149615.doc 13 201111345 所述裝置(例如〇LED或顯示器裝置)中之用途。 如結合附圖進行閱讀’在審閱本發明之以下說明(包括Arn is independently as defined above for Αγ5; each of d, e, f, g, h&i is independently as defined above; j is independently as defined above for d; and k is independently Is as defined above for e; 149615.doc -11- 201111345 and wherein it is selected from (Ar4)d(Ar5)e, (Ar6)f(Ar7)g, (Ar8)h(Ar9)i and (Αη〇ΜΑΓ" At least three of ΑΓ5, ΑΓ7, Ar9 and Ari丨 are each independently an electron-deficient aryl group, an aryl-ethylene group or an aryl-exetylene group, and are optionally substituted. In still another aspect, the invention provides an oligomer or polymer comprising two or more units derived from a compound as described herein. In still another aspect, the invention provides a dendrimer comprising two or more units derived from a compound as described herein. In still another aspect, the invention provides a light emitting device comprising a compound as described herein. In another aspect, the invention provides an electroluminescent device comprising a compound as described herein. In a related aspect, the invention provides an organic light emitting diode (OLED;) comprising a compound as described herein. In another aspect, a film comprising a compound as described herein is provided. In yet another aspect, a device comprising an anode, a cathode, and a film as described herein is provided, the film being disposed between the anode and the cathode. In yet another aspect, a device is provided comprising: an anode; an emissive layer disposed on the anode, the emissive layer comprising a compound as described herein; and a cathode disposed on the emissive layer. In another aspect, the invention provides a device comprising an emissive layer, wherein the emissive layer comprises a compound or film as described herein. In another aspect, a device is provided, comprising: an anode; a hole transport layer disposed on the anode of the anode 149615.doc •12·201111345; an emission layer disposed on the hole transport layer; disposed on the emission layer And an electron transport layer; and a cathode disposed on the electron transport layer; wherein at least one of the hole transport layer, the emissive layer, and the electron transport layer comprises a compound or film as described herein. In still another aspect, a device is provided, comprising: an anode; a hole injection layer disposed on the anode; a hole transport layer disposed on the hole injection layer, and an emission disposed on the hole transport layer a layer; an electron transport layer disposed on the emissive layer; and a hole blocking layer disposed on the electron transport layer; an electron injecting layer disposed on the emissive layer; a cathode disposed on the electron injecting layer; At least one of the hole transport layer, the emissive layer, or the electron transport layer comprises a compound or film as described herein. In still another aspect, the invention provides a photovoltaic cell comprising an active layer, wherein the active layer comprises a compound or film as described herein. In yet another aspect, the invention provides a chemical or biological sensor comprising a sensing layer, wherein the 6-well sensing layer comprises a compound or film as described herein. Suitably, the devices referred to herein are display devices, such as display panels. Accordingly, yet another aspect of the present invention provides a display device comprising a compound or film as described herein. In a still further aspect, the invention provides a method of preparing a compound as described herein. In a still further aspect, the invention provides a method of making a device (e.g., an OLED or display device) as described herein. In a still further aspect, the invention provides the use of a compound as described herein in a device (e.g., a 〇LED or display device) as described herein in 149615.doc 13 201111345. Read as read in conjunction with the figures' in the following description of the invention (including
各實例)後,業内一般技術人員將明瞭本發明之其 及特徵。 、心A 該等態樣中之任-者皆可與其他態樣中之任—者或多者 組合’與-個態樣相關之可選及較佳特徵適宜應用於其他 I、樣中之任-者。具體而言,參照方法或S途所闡述之特 徵亦適宜應用於產物(化合物、裝置等)且反之亦然。 【實施方式】, 本文所述化合物之實施例可電致發光,此意味著當電流 經過此等化合物時其可發射光。因此,此等化合物適合用 於有機電子裝置中之電荷傳輸層或發光層中。 方便地,如本文所述化合物係由化合物核心中之電洞傳 輸部分及至少三個自該核心延伸之臂組成,每一臂皆包含 電子傳輸部分。結構特徵之此組合*僅賦予化合物雙極傳 輸力月b f生,而且達成平衡電荷傳輸性質。適宜地,當將化 口物納入發光裝置中時此提供良好之裝置性能。具體而 言,如本文所闡述及闡釋,藉由採用本文所述組份之特定 排列可有利地改變(例如視需要增加、或減少或消除)色純 度、發射紅移、裝置效率、裝置壽命及驅動電壓中之—者 或多者。此外,適宜地’此等化合物係溶液可處理的,且 可容易地將其純化至相對較高程度。因此,各實施例可解 决上文所述問題並提供(例如)在OLED中表現良好之化合 物。 149615.doc •14· 201111345 因此,在-個態樣中’本發明提供化合物 (1)電洞傳輪核心部分,今 ^ 八 °亥電㈣輪核心部分包含三級氮部 刀’)至少三個電子傳輸臂部分,其自該核心延伸,每 一電子傳輸臂部分皆包含電子傳輪部分及發射部分。 :二,該化合物包含(3)至少一個額外臂部分。在各 =:,該(等:額外臂中之至少一者包含帶隙大於該 彳輸臂之该發射部分之帶隙的發射部分。此排列 、且地確保發射僅自電子傳輸臂之該發射部分(如上文所 說明’其通常係存於與缺電子部分相同之 不會自額外臂上之發射部分發生。 )“ 電洞傳輸部分、電子傳輸臂部分、電子傳輪部分及(若 存在)額外臂部分係如本文所述適宜地選擇。 夕較佳地,臂部分(電子傳輸及額外)之總數量為4或更 多、5/更多、6或更多、或1〇或更多。通常,臂部分之最 大數量為100 ’較佳為50,且最佳為2〇。臂部分可直接地 ^間接地連接至電洞傳輸核心部分。在各實施例中,臂部 刀中之—些或全部係具支鏈結構之一部分。化合物之 周圍(非核)部分可具支鏈且適宜地,該等支鏈中之一些 或全部包含臂部分。 符合此設計之化合物適宜地允許降低分子内偶極矩。此 外:匕具有因存在三個或更多個臂而產生之龐大結構之化合 方止刀子彼此罪近,藉此可有效地減少分子間相互作 用。分子内偶極矩及分子間相互作用之減少適宜地達成 裝置之咼效率且可避免發射光譜紅移之副作用。 149615.doc 201111345 ”體而。I發明實施例藉由提供具有三個或更多個臂 之又極化σ物可解決上文所論述之缺點,纟中電洞傳輸功 此提供於核〜中且電子傳輸功能分佈於在三個或更多個周 圍臂中。 因此’例如藉由在發射層中提供如本文所述化合物,可 將電洞及電子:者注人發射層中並使其在發射層中傳輸。 具體而言’藉由提供三個或更多個周圍臂,本發明者已 達成平衡電荷傳輪性質問題之顯著改良。特定而言,本發 明者已發現在此等臂中放置缺電子基團結合核心中之含有 三級氮之部分(例如三芳基胺)可顯著降低化合物之偶極 矩。 田#圍、-堯核〜貫質上對稱地排列及/或實質上均勻地間 隔開時此方法尤其有效。就此而言,本文所提及圍繞核心 ,該等對稱排列及/或均勾間隔開將為熟習此項技術之閱 讀者所理解且適宜地關於f圍繞核心、之排列以便在假定每 漳之尺寸及形狀相同之情況下,當化合物以正常方式繪 —或圍"堯核〜之臂的分佈以規則間隔、較佳以相鄰臂 或臂群組之間之實f上相同角度發生時可識別延伸穿過 一組臂中之一個臂之一或多條對稱線。 此外本發明者已發現藉由提供三個或更多個圍繞電洞 傳輸核心之臂,能夠更有效地調整或「微調」化合物之電 子傳輪特性。舉例而言,此可藉由調節該等臂中僅一者之 電子傳輸部分及/或在不同臂中提供不同電子傳輪部分來 達成。 149615.doc -16- 201111345 另一優點係提供三個或更多個臂允許可促成化合物偶極 矩之基團之更平衡分佈。藉此,(例如)藉由改變該等臂申 僅一者或一些之組份或取代基可更容易地對偶極矩進行調 節。較佳地,化合物之偶極矩在〇至5德拜(debye)範圍内、 較佳為0至4德拜、較佳為〇至3.5德拜且最佳為〇至3 25德 拜。 在各實施例中,該等臂中之一者或多者(例如全部)之結 構足夠龐大以幫助減少或阻止分子間相互作用。因此,本 文所述化合物之設計可適宜地增強發光材料之顏色穩定 性、尤其對於藍光發射應用而言且具體而言對於基於苐之 發光材料而言。 如本文所述發光化合物可用於發光裝置之發射層中或 作為摻雜物用於此一裝置中之適宜層中。又一用途係作為 電致發光發光二極體之主體材料。可(例如)藉助溶液製程 將本文所定義化合物製作成led裝置。 適宜地,化合物發射藍色、綠色、紅色或白色的光。 較佳地,化合物係藍色發光化合物。適宜地,化合物在 400 nm至495 nm範圍内、較佳4〇〇 11〇1至48〇 nm之波長下發 射光適且地,最大發射波長小於450 nm、較佳小於44〇 ㈣、較佳小於43〇 nm且最佳小於42〇⑽。尤佳之範圍係 400 nm至 42G nm、較佳係彻 nm至 415 nm。 在其他實施例中,化合物係綠色發光化合物。 在其他實施例中,化合物係紅色發光化合物。 在其他實施例中’化合物係白色發光化合物。 149615.doc -17· 201111345 可调即臂部分之發射部分以產生期望顏色輸出。提供三 或更夕個臂之優點在於可提供更具撓性之發射部分。在 ,、中在電子傳輸臂部分中之—些或全部中發射部分晚鄰缺 電子部分之實施例中,由於發射部分接近缺電子部分可改 良發射效率,故可尤其有效地控制輸出之調節。 氺氺*氺氺 適宜地,化合物具有式I之結構:The various features and advantages of the present invention will become apparent to those skilled in the art. , the heart A, any of the other aspects can be combined with any of the other aspects - or a combination of multiple - and - the characteristics of the optional and preferred features are suitable for use in other I, Anyone. In particular, the features set forth in the reference method or S-way are also suitable for use in products (compounds, devices, etc.) and vice versa. [Embodiment] Embodiments of the compounds described herein can be electroluminescent, which means that they can emit light when current passes through such compounds. Therefore, these compounds are suitable for use in a charge transport layer or a light-emitting layer in an organic electronic device. Conveniently, the compound as described herein consists of a hole transport portion in the core of the compound and at least three arms extending from the core, each arm comprising an electron transport portion. This combination of structural features* only imparts bipolar transmission force to the compound and achieves balanced charge transport properties. Suitably, this provides good device performance when the chemistry is incorporated into the illuminating device. In particular, as set forth and illustrated herein, color purity, red-shift, device efficiency, device lifetime, and/or device lifetime can be advantageously varied (eg, increased, decreased, or eliminated, as needed) by employing a particular arrangement of the components described herein. One or more of the drive voltages. Moreover, suitably such compounds are solution treatable and can be readily purified to a relatively high degree. Thus, embodiments can address the problems described above and provide, for example, compounds that perform well in OLEDs. 149615.doc •14· 201111345 Therefore, in the present invention, the present invention provides the core portion of the compound (1) hole-passing wheel, and the core portion of the current eight-eighth electric (four) wheel contains a three-stage nitrogen knife') at least three An electron transfer arm portion extending from the core, each electron transfer arm portion including an electron transfer portion and a launch portion. : Second, the compound comprises (3) at least one additional arm portion. At each =:, the (equal: at least one of the additional arms includes an emission portion having a band gap greater than a band gap of the transmitting portion of the 彳 arm. This arrangement ensures that the emission is only emitted from the electron transport arm The part (as explained above) is usually stored in the same part as the electron-deficient part and does not occur from the emission part of the extra arm.) "Cave transmission part, electron transfer arm part, electron transfer part and (if present) The extra arm portion is suitably selected as described herein. Preferably, the total number of arm portions (electron transmission and extra) is 4 or more, 5/more, 6 or more, or 1 or more. Typically, the maximum number of arm portions is 100', preferably 50, and most preferably 2. The arm portion can be directly and indirectly connected to the hole transport core portion. In various embodiments, the arm portion is One or all of the parts of the branched structure. The surrounding (non-nuclear) portion of the compound may be branched and, suitably, some or all of the branches comprise the arm portion. Compounds consistent with this design suitably permit the reduction of the molecule Inner dipole moment. In addition: cookware There is a large structure of the knives due to the presence of three or more arms, and the knives are close to each other, thereby effectively reducing the intermolecular interaction. The reduction of the intramolecular dipole moment and the intermolecular interaction is suitably achieved. The efficiency of the device is 且 and the side effects of the red shift of the emission spectrum can be avoided. 149615.doc 201111345 ” The invention embodiment solves the above discussion by providing a re-polarized σ with three or more arms. Disadvantages, the transmission of the hole in the crucible is provided in the core ~ and the electron transport function is distributed in three or more surrounding arms. Thus, for example, by providing a compound as described herein in the emissive layer, electricity can be Holes and electrons are injected into the emitter layer and transported in the emissive layer. Specifically, by providing three or more surrounding arms, the inventors have achieved significant improvements in the problem of balanced charge transfer properties. In particular, the inventors have discovered that the placement of an electron-deficient group in such arms in combination with a tertiary nitrogen-containing moiety (e.g., a triarylamine) in the core can significantly reduce the dipole moment of the compound. This method is particularly effective when the symmetry is arranged symmetrically and/or substantially evenly spaced. In this regard, the symmetry of the arrangement and/or the spacing of the bars around the core will be familiar to the art. It is understood by the reader and is suitably arranged around the core, so that when the size and shape of each raft are assumed to be the same, when the compound is drawn in a normal manner - or the distribution of the arm of the 尧 〜 〜 is regularly spaced Preferably, one or more lines of symmetry extending through one of the set of arms are identified when the same angle occurs between the adjacent arms or groups of arms. The inventors have discovered that by providing Three or more arms around the hole transport core can more effectively adjust or "fine tune" the electron transfer characteristics of the compound. For example, this can be done by adjusting the electron transport portion of only one of the arms. And/or providing different electronic transfer portions in different arms to achieve. 149615.doc -16- 201111345 Another advantage is that providing three or more arms allows for a more balanced distribution of groups that can contribute to the dipole moment of the compound. Thereby, the dipole moment can be more easily adjusted, for example, by changing the composition or substituent of only one or some of the arms. Preferably, the compound has a dipole moment in the range of 〇 to 5 debye, preferably 0 to 4 debye, preferably 〇 to 3.5 debye and most preferably 〇 to 3 25 debye. In various embodiments, the structure of one or more (e.g., all) of the arms is sufficiently large to help reduce or prevent intermolecular interactions. Thus, the design of the compounds described herein may suitably enhance the color stability of the luminescent material, especially for blue light emitting applications and in particular for germanium based luminescent materials. The luminescent compound as described herein can be used in the emissive layer of a light-emitting device or as a dopant in a suitable layer in such a device. Another use is as a host material for an electroluminescent diode. The compounds defined herein can be made into a LED device, for example, by means of a solution process. Suitably, the compound emits light of blue, green, red or white. Preferably, the compound is a blue luminescent compound. Suitably, the compound emits light at a wavelength in the range of 400 nm to 495 nm, preferably 4 〇〇 11 〇 1 to 48 〇 nm, and the maximum emission wavelength is less than 450 nm, preferably less than 44 〇 (4), preferably Less than 43 〇 nm and optimally less than 42 〇 (10). The preferred range is from 400 nm to 42 G nm, preferably from nm to 415 nm. In other embodiments, the compound is a green luminescent compound. In other embodiments, the compound is a red luminescent compound. In other embodiments the compound is a white luminescent compound. 149615.doc -17· 201111345 Adjustable is the emission part of the arm part to produce the desired color output. The advantage of providing three or more arms is that a more flexible launch portion can be provided. In the embodiment in which some or all of the electron transfer arm portions emit a portion of the late electron-deficient portion, since the emission portion is close to the electron-deficient portion, the emission efficiency can be improved, so that the adjustment of the output can be particularly effectively controlled.氺氺*氺氺 Suitably, the compound has the structure of formula I:
(I) 其中: 核心部分Q包含至少一個含有三級氮之部分,其視情 況經取代; 、(I) where: core portion Q contains at least one portion containing tertiary nitrogen, which is replaced as appropriate;
臂部分GH y及αΐ]中之每—者獨立地包含 芳基、芳基伸乙稀基或芳基伸乙炔基,且視情況經取代; 且 1496I5.doc •18- 201111345 η、p及q中之每一者獨立地為】至5〇 且其中 X等臂刀中之至少三者係電子傳輸臂部分且獨立地包 含發射部分及可視情㈣取代之缺電衫基、芳基伸乙辦 基或芳基伸乙炔基。 根據式卜該化合物具有至少三個臂㈣+抑。適宜 地’該等臂部分係實質上對稱_繞該核心部分排列。 選自任-次出現的B,、m3之…者或多 一者或多者及B3中一者哎多去夕& ζ Α .者之任—組合皆可提供所需缺 電子基團。 而财 適宜地,至少一個Bl、至少_ 個b2及至少一個B提供所 需缺電子基IS。 適宜之發射部分已為熟習此 1…為此項技術之讀者所知且實 在本文中予以論述。 適宜地,該等臂部分中之至 夕者(例如出現至少一次 的Β2)包含帶隙大於電子傳輸臂 执奇。Ρ分之該發射部分之帶隙 的補充發射部分。 μ * * * * 通常’三級氮部分選自氮、-μ 、曰虱二方基胺及聚(芳基胺基) 宜地,核心部分包含一個、兩彳 ILJ、二個或更多個三級氮 在各實施例中,三級氮部八 卩分適宜地具有式N(Ar (Ar)2-N-(Ar)-N-(Ar)2,其 + 每—比Each of the arm portions GH y and α ΐ] independently comprises an aryl group, an aryl extended ethylene group or an aryl extended ethynyl group, and is optionally substituted; and 1496I5.doc • 18- 201111345 η, p and q Each of them is independently up to 5 〇 and at least three of the X-arm knives are part of the electron-transporting arm and independently comprise the emitting part and the illuminating base, the aryl-based base or the fang Exoacetylene group. According to the formula, the compound has at least three arms (four) + inhibit. Suitably, the arm portions are substantially symmetrical about the core portion. Any one or more of B, m3, or more than one of B3, and one of B3's eves and ; Α can provide the desired electron-deficient group. Suitably, at least one Bl, at least _b2, and at least one B provide the required electron-deficient IS. Suitable emitting portions are well known to those skilled in the art and are discussed herein. Suitably, the eve of the arm portions (e.g., Β2 occurring at least once) includes a band gap greater than the electron transport arm. The supplementary emission portion of the band gap of the transmitting portion is divided. μ * * * * Usually 'the tertiary nitrogen moiety is selected from the group consisting of nitrogen, -μ, bismuth diamine and poly(arylamine). Preferably, the core contains one, two 彳ILJ, two or more Tertiary Nitrogen In each of the examples, the third-order nitrogen octagonal portion suitably has the formula N(Ar(Ar)2-N-(Ar)-N-(Ar)2, which is + per ratio
Ar s係如本文所述獨」 加以選擇。然而,三級氮之數 致里可能更多,例如3個; 多個、4個或更多個、5個或更 尺夕個、或10個或更多個 149615.doc -19- 201111345 氮通㊉每一二級氮皆經三個芳基或伸芳基取代(其中 之一者或多者可依次鍵結至又一氮)。 氺水氺氺氺 藉由提供具有一個或多個三級氮之核心部分(例如三芳 基胺或聚(芳基胺基)),適宜地,可增加化合物之H〇MO能 級,尤其在包含該化合物之〇]1£1)裝置之作業電壓較低時 可促進電洞注入及傳輸。 氺Φ sfe *氺 在含有三級氮之核心0係氮之情形下,該氣適宜地係 直接連接至臂部分,例如如下所示:Ar s is selected as described herein. However, the number of tertiary nitrogens may be more, for example 3; multiple, 4 or more, 5 or more, or 10 or more 149615.doc -19- 201111345 nitrogen Each of the secondary nitrogens is substituted with three aryl or extended aryl groups (one or more of which may be bonded to another nitrogen in turn). By providing a core portion having one or more tertiary nitrogens (for example, a triarylamine or a poly(arylamino group)), suitably, the H〇MO level of the compound can be increased, especially in inclusion The compound 〇]1£1) facilitates hole injection and transmission when the operating voltage of the device is low.氺Φ sfe *氺 In the case of a core 0 series nitrogen containing tertiary nitrogen, the gas is suitably connected directly to the arm portion, for example as follows:
[B3] 氺氺氺氺Φ 適宜地,每一Bl皆獨立地包含C51(H)芳基、C51GG芳基伸 乙烯基或芳基伸乙炔基,較佳c5 8〇芳基、c5 8〇芳基 伸乙烯基或C5-8〇芳基伸乙炔基,且更佳^心芳基、c5 5〇芳 基伸乙烯基或C5.5〇芳基伸乙炔基且視情況經取代。 適宜地,每一B2皆獨立地包含C51⑽芳基、C51⑽芳基伸 乙烯基或C5.100芳基伸乙炔基,較佳C5-8〇芳基、C58〇芳基 伸乙烯基或Cs.so芳基伸乙炔基,且更佳^⑴芳基、C5 5〇芳 基伸乙烯基或(:5_5〇芳基伸乙炔基且視情況經取代。 適宜地,每一h皆獨立地包含C5_i⑽芳基、i⑽芳基伸 149615.doc •20. 201111345 乙烯基或C5-l00芳基伸乙炔基,較佳C5 8〇芳基、C5 8〇芳基 伸乙烯基或C5_8〇芳基伸乙炔基,且更佳C5 5〇芳基、c5 5〇芳 基伸乙烯基或C5_5〇芳基伸乙炔基且視情況經取代。 適宜地,每一Βι皆如下文所述獨立地為(Ar4)d(Ar5)e。 適宜地,每一B2皆如下文所述獨立地為(Ar6)f(Ar7)g。 適宜地,每一B3皆如下文所述獨立地為(ArdJArA。 氺氺氺氺氺 較佳地n、p&q中之每一者獨立地為1至2〇,更佳為丄至 10,更佳為1至5,更佳為1至3且最佳為1或2。 適且地,n+p + qsi〇〇、較佳£5〇、且更佳$1〇 〇 適宜地,該化合物含有4個或更多個、5個或更多個、或 6個或更多個臂部分。因此,在各實施例中,n、口及^中之 一者或多者係2或更多。 可藉由(例如)在連接至核心中三級氮之芳基上提供兩個 或更多個臂使η、Ρ及q中每一者之值皆>1。實例係其中至 少一個連接至氮之芳基經兩個或更多個臂取代之三芳基胺 核心0 另一選擇為或另外,可將連接至含有三級氮之核心(例 如二芳基胺)之芳基中之一者或多者連接至又一含有三級 氮之基團(例如三芳基胺或聚(芳基胺)基團)。 藉此’如上文所論述’可達成臂結構之支化。適宜芳基 及支化之實例將在本文中予以闡述。 氺氺*氺氺 在各實施例中,核心部分〇包含單個三級胺單元或多 149615.doc •21- 201111345 個二級氮單元,例如如式中所示者: r ^ 一一(Arl)a—N—陶^一_ (Ar3)c (la) 其中[B3] 氺氺氺氺Φ Suitably, each Bl independently comprises a C51(H) aryl group, a C51GG aryl vinyl group or an aryl ethynyl group, preferably a c5 8 aryl group, a c5 8 aryl group extending ethylene. Or a C5-8 indenyl ethynyl group, and more preferably a heart aryl group, a c5 5 aryl group, a vinyl group or a C5.5 aryl group ethynyl group, and optionally substituted. Suitably, each B2 independently comprises C51(10)aryl, C51(10)aryl extended vinyl or C5.100 aryl extended ethynyl, preferably C5-8〇aryl, C58〇arylvinyl or Cs.soaryl extended acetylene More preferably, the (1) aryl group, the C5 5 aryl group is a vinyl group or a (5-5 aryl group ethynyl group and optionally substituted. Suitably, each h independently comprises a C5_i(10) aryl group, i(10) aryl group extension 149615 .doc •20. 201111345 Vinyl or C5-l00 aryl ethynyl, preferably C5 8 aryl, C5 8 aryl aryl vinyl or C5_8 aryl ethynyl, and more preferably C5 5 aryl, c5 5〇aryl extended vinyl or C5_5〇aryl ethynyl and optionally substituted. Suitably, each Β is independently (Ar4)d(Ar5)e as described below. Suitably, each B2 is as follows Said independently as (Ar6)f(Ar7)g. Suitably, each B3 is independently (ArdJArA as described below), preferably each of n, p&q Independently 1 to 2 Torr, more preferably 丄 to 10, more preferably 1 to 5, still more preferably 1 to 3 and most preferably 1 or 2. Appropriately, n + p + qsi 〇〇, preferably £5〇 And more preferably $1, suitably, the compound contains 4 or more, 5 or more, or 6 or more arm moieties. Thus, in various embodiments, n, s, and ^ One or more are 2 or more. The value of each of η, Ρ, and q can be made by, for example, providing two or more arms on the aryl group attached to the tertiary nitrogen in the core. All > 1. Examples are triarylamine cores in which at least one aryl group attached to nitrogen is substituted with two or more arms. Alternatively, or in addition, it may be attached to a core containing tertiary nitrogen (eg, One or more of the aryl groups of the diarylamine) are attached to another group containing a tertiary nitrogen group (eg, a triarylamine or poly(arylamine) group). By this, as discussed above. Branching of the arm structure can be achieved. Examples of suitable aryl groups and branching will be set forth herein. 氺氺*氺氺 In each of the examples, the core portion 〇 contains a single tertiary amine unit or more 149615.doc • 21 - 201111345 secondary nitrogen units, for example as shown in the formula: r ^ one (Arl) a - N - Tao ^ _ (Ar3) c (la)
Ar^、AO及Ah中每一者獨立地為伸芳基、伸芳基伸乙烯 基、伸芳基伸乙炔基或胺基伸芳基,且視情況經取代; a、b及c中之每一者獨立地為〇至2〇 ;且 1獨立地為1至2〇。 因此’在一些實施例中,若卜丨且b=〇,則毗鄰三級氮可 共享共用芳基,例如Ar!。 氺*氺水氺 適且地,Ari、Ah及An中之每一者獨立地為C5 i〇〇伸芳 基、⑼伸芳基伸乙烯基、C5_1〇dt芳基伸乙炔基或胺基 C5_l00伸芳基,較佳為C5-5G伸芳基、C5⑼伸芳基伸乙烯 基、_〇5.^伸芳基伸乙炔基或胺基6^伸芳基更佳為c5 3〇 伸芳基Cs-3〇伸芳基伸乙烯基、C5_3〇伸芳基伸乙炔基或胺 基C,3。伸芳基,更佳扣_15伸芳基、C515伸芳基伸乙稀 基' C5-丨5伸芳基伸乙炔基或胺基丨5伸芳基,且視情況經 取代。 適宜地’ Ar丨、Ar2及Ar3中每一者之伸芳基皆獨立地為碳 伸芳基或雜伸芳基。較佳地,Ari、〜及—中每一者之伸 1496I5.doc •22- 201111345 方基皆為碳伸芳基。 適宜地’ Ar〗、Ah及Ar*3中之任兩者係相連的。即,Ari 及Αι*2、或八〜及八!*3、或Ah及An中之任一者或多者較佳適 宜地藉助單鍵或〇、S、Si或視情況經取代之伸烷基(較佳 C1 -3伸烧基)彼此相連。 較佳地ΑΓι、Αι*2及A1·3中之每一者獨立地為伸苯基、伸荞 基伸°卡。坐基、二芳基胺基、螺伸聯第基、螺石夕雜伸聯第 基、茚并伸咔唑基、節并伸苐基或胺基伸芳基且視情況經 取代。 較佳地An、Αι·2及Ar*3中之每一者獨立地為伸苯基或伸苐 基且視情況經取代。 氺%本氺* 在各實施例中,Ari、Ah及中之每一者獨立地為經咔 唑基取代之伸苯基且視情況進一步經取代,適宜地如下所 示:Each of Ar^, AO and Ah is independently an extended aryl group, an extended aryl group vinyl group, an aryl ethynyl group or an amine group aryl group, and optionally substituted; each of a, b and c Independently 〇 to 2〇; and 1 is independently 1 to 2〇. Thus, in some embodiments, if 丨 and b = 〇, the adjacent ternary nitrogen may share a common aryl group, such as Ar!.氺*氺水氺 Appropriately, each of Ari, Ah, and An is independently C5 i〇〇 aryl, (9) aryl extended vinyl, C5_1〇dt aryl ethynyl or amine C5_l00 The group is preferably a C5-5G aryl group, a C5(9) aryl group, a vinyl group, a 〇5. aryl acetylene group or an amine group 6 aryl group, preferably a C5 3 〇 aryl group Cs-3〇 The aryl group is a vinyl group, a C5_3 aryl group ethynyl group or an amine group C, 3. More aryl, more preferably -15 extended aryl, C515 extended aryl extended ethylene 'C5-丨5 extended aryl ethynyl or amine 丨5 extended aryl, and replaced as appropriate. Suitably, the extended aryl groups of each of 'Ar丨, Ar2 and Ar3 are independently a carbon-extended aryl group or a hetero-aryl group. Preferably, the extension of each of Ari, 〜, and - 1496I5.doc • 22- 201111345 is a carbon aryl group. Suitably, either Ar', Ah, or Ar*3 are connected. That is, any one or more of Ari and Αι*2, or VIII~ and 八!*3, or Ah and An are preferably suitably treated with a single bond or hydrazine, S, Si or optionally substituted alkylene. The groups (preferably C1 -3 extension groups) are connected to each other. Preferably, each of ΑΓι, Αι*2, and A1·3 is independently a phenyl group and a 荞 base. The pendant group, the diarylamine group, the spiro-extension group, the spiro-indene extension unit, the hydrazine and the carbazolyl group, the fluorenyl group or the amine group aryl group, and optionally substituted. Preferably, each of An, Αι·2 and Ar*3 is independently a phenyl or thiol group and is optionally substituted.氺%本氺* In each of the examples, each of Ari, Ah, and each is independently a phenyl group substituted phenyl group and further substituted as appropriate, suitably as follows:
在各實施例中"卡唾基係在3位及6_位中之—者或兩者 處鍵結,適宜地如下所示: 149615.doc -23. 201111345In each of the embodiments, the " cardinal system is bonded at - or both of the 3 and 6_ positions, suitably as follows: 149615.doc -23. 201111345
在各實施例中,Ari、ΑΓ2&Αι_3中之每一者獨立地為伸第 基且視情況經取代,適宜地如下所示:In various embodiments, each of Ari, ΑΓ2 & Αι_3 is independently a stretched base and is optionally substituted, suitably as follows:
通吊’ Ar!、Αΐ"2及Α1·3中之每一者獨立地為經取代之伸第 基’較佳在9-位經取代,適宜地如下所示:Each of the hangers 'Ar!, Αΐ"2 and Α1·3 is independently substituted with a substituted base. Preferably, it is substituted at the 9-position, suitably as follows:
較佳地’ Ar!、Ah及Ar*3中之每一者獨立地為經取代之伸 薙基’較佳在9-位經二取代,適宜地如下所示:Preferably, each of 'Ar!, Ah, and Ar*3 is independently a substituted thiol', preferably disubstituted at the 9-position, suitably as follows:
基,更佳係C3_8烷基,更佳係C5.7烷基且最佳係c6烷基,且 該烷基取代基視情況經取代。 在尤佳實施例中,Ar,、AO及Ah中之每一者獨立地為 149615.doc -24- 201111345More preferably, it is a C3-8 alkyl group, more preferably a C5.7 alkyl group and most preferably a c6 alkyl group, and the alkyl substituent is optionally substituted. In a particularly preferred embodiment, each of Ar, AO, and Ah is independently 149615.doc -24- 201111345
適宜地,ΑΓι、入^及入^相同。然而,在其他實施例中, Ar!、Ar2及 Ar3 不同。 較佳地’ a、1^及c中之每一者獨立地為1至2〇,更佳為】 至10’更佳為1至5,更佳為1至3且最佳為1或2。 在各實施例中,a、b及c相同。在其他實施例令,並非 所有a、b及c均相同。在一些實施例中,所有a、^均不 同0 氺氺氺氺* 適宜地’核心部分係式1b之三芳基胺: (Ar,)aSuitably, ΑΓι, enter ^ and enter ^ are the same. However, in other embodiments, Ar!, Ar2, and Ar3 are different. Preferably, each of 'a, 1^ and c is independently from 1 to 2, more preferably from 10 to more preferably from 1 to 5, more preferably from 1 to 3 and most preferably from 1 or 2. . In each of the examples, a, b, and c are the same. In other embodiments, not all of a, b, and c are the same. In some embodiments, all a, ^ are different from 0 氺氺氺氺 * suitably 'core portion of the triarylamine of formula 1b: (Ar,)a
I 八 (A「2)b (A「3)c (lb) 其中 Αγ!、Ah及Αι*3中之每一者獨立地係如上文所定義;且 a、b及c中之每一者獨立地係如上文所定義。 適宜地’ Ar]、Ar*2及Ar3中之每一者皆如本文所述係直接 地或間接地鍵結至臂部分。 在各貫施例中’ An、Arj及Ar3中之一者或多者獨立地為 胺基芳基且較佳地該胺基芳基具有結構_(Ari,)_ 149615.doc -25- 201111345 N(Ar2’)(Ar3’),其中Arr、Ar2·及Ar3.中之每一者獨立地係如 上文分別針對Ari、Ar2及Ar3所定義。適宜地,Arr、Ar2. 及Ar3_中之一者或兩者、較佳地Arr及A1·3,中之一者或兩者 係如本文所述獨立地鍵結至臂部分。 氺氺窣氺* 因此,在一個實施例中,核心部分〇係式1()之包含兩 個三級氮之聚(芳基胺): (Ar,)aI 八(A "2)b (A "3)c (lb) where Αγ!, Ah, and Αι*3 are each independently as defined above; and each of a, b, and c Independently as defined above. Suitably each of 'Ar', Ar*2 and Ar3 is bonded directly or indirectly to the arm portion as described herein. In each embodiment, 'An, One or more of Arj and Ar3 are independently an aminoaryl group and preferably the aminoaryl group has a structure _(Ari,)_ 149615.doc -25- 201111345 N(Ar2')(Ar3') , wherein each of Arr, Ar2, and Ar3. is independently defined as above for Ari, Ar2, and Ar3. Suitably, one or both of Arr, Ar2., and Ar3_, preferably, One or both of Arr and A1·3 are independently bonded to the arm portion as described herein. 氺氺窣氺* Thus, in one embodiment, the core portion of the formula 1() contains two a three-stage nitrogen poly(arylamine): (Ar,)a
(Ar2)b(Ar2)b
(ΑΓ3')0· (ΑΓ3··)0· (Ic) 其中 A1*3獨立地係如上文所定義;(ΑΓ3')0· (ΑΓ3··)0· (Ic) where A1*3 is independently as defined above;
Ai*3’及Αι*3"中之母一者獨立地係如上文針對ΑΓ〗所定義; a、b及c中之每一者獨立地係如上文所定義;且 c’及c’’中之每一者獨立地係如上文針對^所定義; 在此一排列中,適宜地’ A1·3、Λα及Ar·3"獨立地不為胺 基芳基。 藉此,An、Αι*2、Al>及ΑΓ3"中之任三者或更多者可直接 地或間接地鍵結至臂部分。 氺«氺*氺 較佳地’該化合物包含式π之結構: 149615.doc •26· 201111345 (ArOaCB,), (B2)P(Ar2)i (Ar3)c(B3)q (II) 其中:The mothers of Ai*3' and Αι*3" are independently as defined above for ΑΓ; each of a, b and c is independently as defined above; and c' and c'' Each of them is independently as defined above for ^; in this arrangement, suitably 'A1·3, Λα and Ar·3" are independently not an aminoaryl group. Thereby, any three or more of An, Αι*2, Al>, and ΑΓ3" can be directly or indirectly bonded to the arm portion.氺«氺*氺 Preferably the compound comprises a structure of the formula π: 149615.doc •26· 201111345 (ArOaCB,), (B2)P(Ar2)i (Ar3)c(B3)q (II) where:
Ar!、Ai*2及Ar*3中之每一者獨立地係如上文所定義; B!、B2及B3申之每一者獨立地係如上文所定義; a、13及c中之每一者獨立地係如上文所定義;且 η ' ?及q中之每一者獨立地係如上文所定義; 且其中·· 選自(B山、⑺水及(A、之至少三個1各自獨立地包含 發射部分及可視情況經取代之缺電子芳基、芳基伸乙烯基 或芳基伸乙炔基。 因此,該至少三個缺電子(即電子傳輸)部分可由任一次 出現的Bl、Β4Β3提供。換言之,該至少三個&中之任一 者可為Βι、Β2及&中之任一者。 車乂佳地。亥至;二個Βχ中之至少—者包含發射部分。 、且也至ν㈤另外的Βι、β2*Β3包含帶隙大於該發 射部分之帶隙的補充發射部分。 似.匕纟°亥等化合物中,電洞傳輸功能係由以下部分提 (Αγ,)3 如上文所述 149615.doc (Ar2)b ^\Αγ3)ζ 其可包含多個氮中心(例如聚(芳基胺)), 例 -27- 201111345 如符合式la或1(;者。 電子傳輸功能係由該至少三個包含缺電子部分之1提 供。適宜之缺電子部分已為熟習此項技術之讀者所知且實 例將在本文中予以陳述。可藉由使用固有地缺電子/拉電 子之芳基、芳基伸乙烯基或芳基伸乙炔基及/或藉由將拉 電子基團連接至芳基、芳基伸乙烯基或芳基伸乙炔基來達 成電子缺失。 *氺氺氺氺 適宜地,每一 Bl皆獨立地為(Ar4)d(Ar5)e,其中每一 及每一 Ah皆獨立地為伸芳基、伸芳基伸乙烯基或伸芳基 伸乙炔基且視情況經取代;且4及e中之每一者獨立地為i 至20。 較佳地,d及e中之每一者獨立地為丨至1〇,更佳為i至 5,更佳為1至3且最佳為1或2。在各實施例中,d係丨至3且 e係1。 *氺氺:|ΐ氺 適宜地,每一 &皆獨立地為(Ar6)f(Ar7)g,其中每一 A。 及每一皆獨立地為伸芳基、伸芳基伸乙烯基或伸芳基 伸乙快基且視情況經取代;且%中之每—者獨立地:! 至20。 較佳地,f及g中之每一者獨立地為丨至1〇 ,更佳為1至 5,更佳為1至3且最佳為〗或2。在各實施例令,f係1至3且 g係1。 149615.doc 28- 201111345 適宜地’每一 B3皆獨立地為(AwjArA,其中每一 及每一 A1·9皆獨立地為伸芳基、伸芳基伸乙烯基或伸芳基 伸乙炔基且視情況經取代;且1!及i中之每一者獨立地為工 至20。 較佳地,h及i中之每一者獨立地為i至1〇,更佳為i至 5,更佳為1至3且最佳為1或2。在各實施例中,^^係丨至3且 i係1。 氺氺氺氺氺 較佳地,化合物具有式ΠΙ之結構: [(Ar4)d(+Ar5)e]n [Ari]a N.Each of Ar!, Ai*2, and Ar*3 is independently as defined above; each of B!, B2, and B3 is independently as defined above; each of a, 13 and c One is independently as defined above; and each of η ' ? and q is independently as defined above; and wherein ... is selected from (B, (7) water and (A, at least three of 1) Each independently comprises an emitting moiety and optionally substituted electron-deficient aryl, arylvinyl or aryl ethynyl group. Thus, the at least three electron-deficient (ie, electron-transporting) moieties can be provided by any of B1, Β4Β3 In other words, any of the at least three & may be any of Βι, Β2, and & 乂 佳佳. Hai to; at least one of the two — includes the transmitting portion. Also to ν(5), the other Βι, β2*Β3 includes a complementary emission portion having a band gap larger than the band gap of the emission portion. In a compound such as 匕纟°海, the hole transmission function is extracted by the following part (Αγ,) 3 as above 149615.doc (Ar2)b ^\Αγ3) ζ which may contain multiple nitrogen centers (eg poly(arylamine)), Example-27- 201111345 if conforming to la or 1 (the electronic transmission function is provided by the at least three electronically deficient portions). Suitable electronic missing portions are known to those skilled in the art and examples will be given herein. Stated by using an inherently electron-deficient/electron-free aryl, arylvinyl or aryl ethynyl group and/or by linking an electron withdrawing group to an aryl group, an arylvinyl group or an aryl ethynyl group To achieve electron loss. *氺氺氺氺 suitably, each Bl is independently (Ar4)d(Ar5)e, wherein each and each Ah is independently an aryl group, an aryl group or a vinyl group. An ethynyl group and optionally substituted; and each of 4 and e independently is from i to 20. Preferably, each of d and e is independently from 1 to 1, more preferably I to 5, more preferably 1 to 3 and most preferably 1 or 2. In each of the examples, d is 丨 to 3 and e is 1. *氺氺:|ΐ氺 suitably, each & The ground is (Ar6)f(Ar7)g, wherein each A and each are independently an aryl group, an aryl group or a aryl group, and optionally Substituted; and each of % is independently: ! to 20. Preferably, each of f and g is independently from 1 to 5, more preferably from 1 to 5, more preferably from 1 to 3. And preferably, or 2. In each embodiment, f is 1 to 3 and g is 1. 149615.doc 28- 201111345 suitably 'each B3 is independently (AwjArA, each and every A1 9 is independently an extended aryl group, an extended aryl group or an aryl group ethynyl group, and is optionally substituted; and each of 1! and i independently works for 20. Preferably, each of h and i is independently i to 1 〇, more preferably i to 5, more preferably 1 to 3 and most preferably 1 or 2. In various embodiments, ^^ is tied to 3 and i is 1. Preferably, the compound has the structure of the formula: [(Ar4)d(+Ar5)e]n [Ari]a N.
[Ar2]b [Ar3]c / \ [(Ar6)KAr7)9]p [(Are)h(Ar9)i]q (III) 其中[Ar2]b [Ar3]c / \ [(Ar6)KAr7)9]p [(Are)h(Ar9)i]q (III) where
Ar!、Ai*2及At*3係如上文所定義;且 a、b、c、η、p&q中之每一者皆係如上文所定義; 且其中Ar!, Ai*2, and At*3 are as defined above; and each of a, b, c, η, p&q is as defined above;
Ar4、Ar5 ' Ar6、Ar7、Ar8及Ar9中之每一者獨立地係如 上文所定義; d、 f及h中之每一者獨立地係如上文所定義;且 e、 g及i中之每一者獨立地係如上文所定義; 且其中 149615.doc -29· 201111345 選自[(Ar4)d(Ar5)e]n、[(Ar6)f(Ar7)g]p 及[(Ar8)h(Ar9)i]e Ar*5 Ar?及Ars»中之至少二者各自獨立地包含缺電子芳基、 芳基伸乙烯基或芳基伸乙炔基。 因此,該至少三個缺電子(即電子傳輸)部分可由任一次 出現的、Ar7或Arg提供。 ***** 適宜地,An' ^6及&8中之每一者獨立地為c5i〇〇伸芳 基、〇5-100伸芳基伸乙烯基或〇5·ι〇〇伸芳基伸乙炔基,較佳 為c5.5。伸芳基、(:5·5。伸芳基伸乙縣或伸芳基伸乙快 基,更佳為(^⑴伸芳基、伸芳基伸乙烯基或◦伸芳 基伸乙炔基,且最佳為P 站it* ^ ^ 且取住為〇5_丨5伸方基、C5丨5伸芳基伸乙烯基 或C5·〗5伸芳基伸乙炔基,且視情況經取代。 I且地A1·4、Are及Ars中每一者之伸芳基皆獨立地為碳 伸芳基或雜伸芳基。 在Ar4、A。及Ars中任一者或多者之伸芳基係雜伸芳基之 It形下D亥雜伸芳基可含有一個或多個選自〇、S、N、Si 及P、較佳-個或多個選自〇、UN、更佳一個或多個選 自〇及N、且最佳為1^的雜原子。 適宜地,若 ^ 4 ^6及&8中任一者或多者之伸芳基係雜 申芳7貝K亥雜伸芳基含有—個、兩個、三個或四個雜原 子右存在複數個雜原子,則該等雜原子可相同或不同。 較佳地,Ar * „ . 4、Ah及Aq中每一者之伸芳基皆係碳伸芳 基。 各對Ar基團Ar4與Ar5、Ar6與Ar7、及Ar8與Ar9 149615.doc -30- 201111345 中之任—者或多者係藉助單鍵或Ο、S、Si或視情況經取代 之伸烷基(較佳Cw伸烷基)彼此相連。 *較佳地,An、Are及Ars中之每一者獨立地為伸苯基、伸 第基伸°卡°坐基、二芳基胺基、螺伸聯第基、螺碎雜伸聯 第基、節并料°坐基、節并伸第基或胺基芳基且視情況經 取代。 較佳地,Ar4、Ar6及Ar8中之每一者獨立地為伸第基且視 情況經取代’適宜地如下所示:Each of Ar4, Ar5 'Ar6, Ar7, Ar8, and Ar9 is independently as defined above; each of d, f, and h is independently as defined above; and in e, g, and i Each of them is independently as defined above; and wherein 149615.doc -29· 201111345 is selected from [(Ar4)d(Ar5)e]n, [(Ar6)f(Ar7)g]p and [(Ar8) At least two of h(Ar9)i]e Ar*5 Ar? and Ars» each independently comprise an electron deficient aryl group, an arylvinyl group or an aryl ethynyl group. Thus, the at least three electron-deficient (i.e., electron transport) portions can be provided by Ar7 or Arg, which occurs at any one time. ***** Suitably, each of An'^6 and &8 is independently c5i〇〇 aryl, 〇5-100 aryl extended vinyl or 〇5·ι〇〇 aryl extension The ethynyl group is preferably c5.5. Stretching aryl, (:5·5. 延芳基伸乙县 or 延芳基伸乙快基, more preferably (^(1) aryl, aryl extended vinyl or aryl extended ethynyl, and the best P station it* ^ ^ and taken as 〇5_丨5 stretch square, C5丨5 extended aryl extended vinyl or C5·〗 5 extended aryl extended ethynyl group, and substituted as appropriate. I and ground A1·4 The exoaryl group of each of Are, and Ars is independently a carbon aryl group or a heteroaryl group. The aryl group heteroaryl group in any one or more of Ar4, A, and Ars The D-heteroaryl group may have one or more selected from the group consisting of ruthenium, S, N, Si and P, preferably one or more selected from the group consisting of ruthenium, UN, more preferably one or more selected from the group consisting of N, and preferably a hetero atom of 1 ^. Suitably, if any one or more of ^ 4 ^ 6 and & 8 are extended, the aryl group is a 7-kil Where two, three or four heteroatoms have a plurality of heteroatoms to the right, then the heteroatoms may be the same or different. Preferably, Ar* „. 4, each of the aryl groups of Ah and Aq Carbocyclic aryl groups. Each pair of Ar groups Ar4 and Ar5, Ar6 and Ar7, and Ar8 and Ar9 149615.doc Any one or more of -30-201111345 is connected to each other by a single bond or hydrazine, S, Si or an optionally substituted alkylene group (preferably Cw alkyl group). * Preferably, An, Are And each of the Ars is independently a phenylene group, a stretching base group, a cyclyl group, a diarylamine group, a spiro-extension base group, a snail-dispersed cross-linking group, a knotting material, a seating base, Further, the aryl or aminoaryl group is optionally substituted. Preferably, each of Ar4, Ar6 and Ar8 is independently a stretching group and is optionally substituted as 'suitably as follows:
r之母一者獨立地為經取代之伸第 適宜地如下所示: 通常,Ar4、Ar6及Ar8中之每一 基,較佳在9-位經取代,適宜地,The mother of r is independently substituted and is suitably as follows: Typically, each of Ar4, Ar6 and Ar8 is preferably substituted at the 9-position, suitably,
-母一者獨立地為經取代之伸 適宜地如下所示: 較佳地,Ar4、Ar6及Ar8中之每— 苐基’較佳在9-位經二取代,適官」The parent is independently substituted for the following as follows: Preferably, each of Ar4, Ar6 and Ar8 is preferably substituted at the 9-position, which is suitable for the officer.
你匕2…烧基,更佳係C2 10烷 5-7燒基且最佳係c6烷基,且 尤佳之取代基係院基,較佳係C 基’更佳係c3.8烧基,更佳係c5.7起 該烧基取代基視情況經取代。 149615.doc •31· 201111345 在尤佳實施例中,Ar4、Are及Ars中之每一者獨立地為匕2...alkyl, more preferably C2 10 alkane 5-7 alkyl and preferably c6 alkyl, and a more preferred substituent is a hospital base, preferably a C base 'better c3.8 alkyl Preferably, the alkyl group c5.7 is substituted as the alkyl group substituent. 149615.doc •31· 201111345 In a particularly preferred embodiment, each of Ar4, Are, and Ars is independently
適且地,Αι*4、Αι*6及Ars相同。然而,在其他實施例中, Ar4 ' Ar6&Ar8不同。 適宜地,Ah、Air?及Ah中之每一者獨立地為C5丨〇〇伸芳 基C5-ioo伸芳基伸乙烯基或伸芳基伸乙炔基,較佳 為伸芳基、Cs-3Q伸芳基伸乙烯基或c5-3〇伸芳基伸乙炔 2,且最佳為C5-丨5伸芳基、C5·丨5伸芳基伸乙烯基或(:5_]5伸 芳基伸乙炔基,且視情況經取代。 視需要,且(例如)根據式In,Ars、Ar?及Ar?中之每一者 獨立地係缺電子的。舉例而言,^5、心7及心9中之每一者 獨立地為缺電子。5,。伸芳基、C51。。伸芳基伸乙稀基或 匸5 - 100伸芳基伸乙炔基。 適宜地’電子缺失可藉由提供具有拉電子基團之伸芳美 來達成°因此’伸芳基、伸芳基伸乙稀基或伸芳基伸乙二Appropriately, Αι*4, Αι*6, and Ars are the same. However, in other embodiments, Ar4 'Ar6&Ar8 are different. Suitably, each of Ah, Air® and Ah is independently a C5-extended aryl C5-ioo extended aryl extended or aryl extended ethynyl group, preferably an extended aryl group, a Cs-3Q stretch Aryl extended vinyl or c5-3 aryl extended acetylene 2, and most preferably C5-丨5 extended aryl, C5·丨5 extended aryl extended vinyl or (:5_]5 extended aryl extended ethynyl, and The situation is replaced. If desired, and for example, according to the formula In, each of Ars, Ar?, and Ar? is independently electron-deficient. For example, each of ^5, heart 7, and heart 9 Independently electron-deficient. 5., aryl, C51. aryl extended ethylene or 匸5 - 100 extended aryl ethynyl. Suitably 'electron deletion can be provided by extension with electron withdrawing groups Fangmei came to reach °, therefore, 'stretching aryl, stretching aryl base or extending aryl base
基通常經至少一個拉雷;AA 1拉電子基團取代9適宜之拉電子基團已 為熟習此項技術之讀者所知。實例在本文中給出。 較佳地,每一拉電子基團皆獨立地選自·鹵基、氰基、 =基、㈣、亞硫醯基1醯基及全尤佳者錢 適宜地,Ar5、 A1·7及A1·9中每一者之伸芳基皆 獨立地為碳 149615.doc •32- 201111345 伸芳基或雜伸芳基。 二、广及Ar9中任一者或多者之伸芳基係雜伸芳基之 ^ 〇亥雜伸方基可含有—個或多個選自0、S、Ν、Si 及P、較佳一個或多個選自〇、S及N、更佳一個或多個選 自〇及N且最佳為]^的雜原子。 ^地’若-、Ar7及〜中任—者或多者之伸芳基係雜 伸方f,則該雜伸芳基含有-個、兩個、三個或四個雜原 ^右存在複數個雜原子,則該等雜原子可相同或不同。 八h及A”中之每一者獨立地選自以The base is typically via at least one of the Raleigh; the AA 1 electron withdrawing group is substituted for the appropriate electron withdrawing group and is known to those skilled in the art. Examples are given herein. Preferably, each of the electron withdrawing groups is independently selected from the group consisting of: halo, cyano, =yl, (d), sulfinyl 1 fluorenyl, and all of them are particularly suitable, Ar5, A1·7 and A1. · Each of the 9 aryl groups is independently carbon 149615.doc • 32- 201111345 aryl or heteroaryl. 2. The aryl group of the extended aryl group of any one or more of Ar9 and Ar9 may contain one or more selected from the group consisting of 0, S, Ν, Si and P, preferably One or more heteroatoms selected from the group consisting of ruthenium, S and N, more preferably one or more selected from the group consisting of ruthenium and N and most preferably. ^地的若若, Ar7 and ~中任-- or more of the extended aryl-based heteroscouts f, then the hetero-aryl group contains -, two, three or four miscellaneous ^ right exists in the plural For heteroatoms, the heteroatoms may be the same or different. Each of eighth and A" is independently selected from
較佳地,Ar5、n A , . 團:Preferably, Ar5, n A , .
N—R_N-R_
149615.doc ς •33· 201111345 其中 R、R’、R,,及 r,,,中 生 甲之母一者獨立地為鹵基(尤其_F 或-Cl)、-CN、-NO,、 -CO、亞硫醯基、磺醯基、Ci 2〇烷 基、Cuo全氟烷基、c •2〇燒氧基、C5.5〇^f•基、C5-50伸芳基 伸乙婦基、或C 5 ,。伸笔|^ 0狎方基伸乙炔基,且q係0至ό之整數。 應瞭解,儘管上文茸此—认 丄 Έ上又某些方基繪示為單價或二價,但端視 芳基出現在如本文所述化合物中所’處之背景,彼等基團中 之任-者皆可為單價或二價。此外,某些化合物繪示成將 基團連接至化合物之其餘部分之鍵如同在原子處或跨越一 鍵進入芳基環之中心—般。應瞭解,該繪示意欲代表可在 環上之可用&置藉㈣將特定芳基連接至該化合物之其餘 部分。 較佳地,Aq、Ar?及Ah中每一者之伸芳基皆係碳伸芳 基。 較佳地,Ah、Ah及Ah中之每一者獨立地為伸苯基且視 情況經取代。較佳地,Ars、Ah及Ar9中之每一者獨立地為 經氰基取代之伸苯基。 較佳地,該化合物具有式(IV)之結構: 149615.doc • 34- 201111345149615.doc ς •33· 201111345 where R, R', R, and r,,, the mother of Zhongshengjia, are independently halo (especially _F or -Cl), -CN, -NO, -CO, sulfinyl, sulfonyl, Ci 2 alkyl, Cuo perfluoroalkyl, c • 2 oxime alkoxy, C5.5 〇 ^ f • base, C 5-50 aryl aryl , or C 5 ,. Stretch pen|^ 0 狎 伸 乙 acetylene group, and q is an integer from 0 to ό. It will be appreciated that, although some of the radicals described above are depicted as monovalent or divalent, the terminal aryl groups are present in the context of the compounds described herein, in such groups. Anyone can be either a unit price or a price. In addition, certain compounds are depicted as linking a group to the remainder of the compound as if at the atom or across a bond to the center of the aryl ring. It should be understood that the drawing is intended to represent that the available aryl groups can be attached to the remainder of the compound. Preferably, the extended aryl group of each of Aq, Ar? and Ah is a carbon extended aryl group. Preferably, each of Ah, Ah and Ah is independently a phenylene group and is optionally substituted. Preferably, each of Ars, Ah and Ar9 is independently a phenyl group substituted with a cyano group. Preferably, the compound has the structure of formula (IV): 149615.doc • 34- 201111345
Ar4a及Ar4b中之每一者獨立坫你 词立地係如上文針對Ar4所定義;Each of Ar4a and Ar4b is independent of you. The wording is as defined above for Ar4;
Ar5a及Arsb中之每一者猶古+Jr及, 令领立地係如上文針對Ar5所定義;Each of Ar5a and Arsb is still +Jr and, and the leading position is as defined above for Ar5;
Ar6aA Ar6b中之每-者獨立地係如上文針對仏所定義; 八匕及Ar?b中之每一者獨立地係如上文針對Μ?所定義; ArSa及Am中之每一者獨立地係如上文針對所定義;且 八〜及Ar%中之每一者獨立地係如上文針對Ar9所定義; 且其中 d!及t中之母一者獨立地係如上文針對d所定義; e〗及ez中之每一者獨立地係如上文針對e所定義; 6及&中之每一者獨立地係如上文針對£所定義; gi及g2中之每一者獨立地係如上文針對g所定義; 匕及!!2中之每一者獨立地係如上文針對h所定義;且 卜及iz中之每一者獨立地係如上文針對i所定義; 149615.doc -35- 201111345 且其中 選自(Ar4a)d丨(Ar5a)e丨、(Ar4b)d2(Ar5b)e2、(Ar6a)f丨(Ar7a)g丨、 (Ar6b)f2(Ar7b)g2、(Ar8a)hl(Ar9a)nA(Ar8b)h2(Ar9b)i22Ar5a、Each of Ar6aA Ar6b is independently as defined above for 仏; each of octagonal and Ar?b is independently as defined above for Μ?; each of ArSa and Am is independently As defined above for each; and each of VIII and Ar% is independently as defined above for Ar9; and wherein the parent of d! and t is independently as defined above for d; And each of ez is independently as defined above for e; each of 6 and & are independently defined as above for £; each of gi and g2 is independently as g is defined; 匕 and !! 2 are each independently defined as defined above for h; and each of ib and iz is independently as defined above for i; 149615.doc -35- 201111345 And selected from (Ar4a)d丨(Ar5a)e丨, (Ar4b)d2(Ar5b)e2, (Ar6a)f丨(Ar7a)g丨, (Ar6b)f2(Ar7b)g2,(Ar8a)hl(Ar9a nA(Ar8b)h2(Ar9b)i22Ar5a,
Ar5b、Ar7a、Ar7b、Ar9a& Ar9b中之至少三者各自獨立地為 缺電子芳基、芳基伸乙烯基或芳基伸乙炔基且視情況經取 代。 因此,該至少三個缺電子(即電子傳輸)部分中之每一者 皆可由任一次出現的Ar5a、Ah、、Am、Af9b 提供。 氺* *氺氺 較佳地,化合物具有式(V)之結構:At least three of Ar5b, Ar7a, Ar7b, Ar9a & Ar9b are each independently an electron deficient aryl group, an aryl vinyl group or an aryl ethynyl group and are optionally substituted. Thus, each of the at least three electron-deficient (i.e., electron transport) portions can be provided by Ar5a, Ah, Am, Af9b, which occurs at any one time.氺* *氺氺 Preferably, the compound has the structure of formula (V):
(V) 其中(V) where
Ar4、Ar5、Ar6、Ar7、八1*8及^9中之每一者獨立地係女 上文所定義;Each of Ar4, Ar5, Ar6, Ar7, VIII 1*8, and ^9 is independently female as defined above;
Ar,。獨立地係如上文針對Ar4所定義; 149615.doc •36· 201111345Ar,. Independently as defined above for Ar4; 149615.doc •36· 201111345
Aru獨立地係如上文針對αΓ5所定義; d、e、f、g、h及i中之每一者獨立地係如上文所定義; j獨立地係如上文針對d所定義;且 k獨立地係如上文針對e所定義; 且其中 選自(Ar4)d(Ar5)e 、 (Ar6)f(Ar7)g 、 (ArdJArA 及 (AricOjCAridkiArs、ΑΓ7、Ar9及Ar丨1中之至少三者各自獨 立地為缺電子芳基、芳基伸乙烯基或芳基伸乙炔基且視情 況經取代。 因此’該至少三個缺電子(即電子傳輸)部分中之每一者 皆可由任一次出現的Ar5、Ar7、Ar9及Arn提供。 氺氺氺氺氺 如圖1中所示意性顯示,如本文所述之化合物1〇可為離 散化合物或為寡聚物或聚合物(例如樹形聚合物)中之重複 單元。化合物10包括可提供電洞傳輸功能之含有三級氮之 核心部分12。在一些實施例中,此係三芳基胺,在其他實 施例中存在兩個、三個或更多個氮中心。 化合物10具有三個臂14、16及18。臂可能多於三個,例 如4個、5個或6個或更多個。 該等臂中之每一者皆具有電子傳輸部分,在臂14上其圖 解說明為2〇。在臂I4之情形下,電子傳輸(即缺電子部幻 基團係(Ar5)e,其中ΑΓ5係缺電子的且視情況經一個或多個 拉電子基團取代(該等拉電子基團可提供所需電子缺失卜 臂14亦包括發射部分22,在此實例中,其包含基 M9615.doc -37- 201111345 團-(Ar^。缺電子部分20接近發射部分適宜地幫助裝置效 率。 臂1 6及1 8亦包括各自之電子傳輸部分及發射部分,其分 別圖解說明為特徵24及26。 在各實施例中’(例如)當η、p及q中之任一者大於1時, 臂14、16及18中之每一者皆可具支鏈。 氺氺氺氺氺 適宜地,Ar,、Arla、Arlb、Ar2、Ar2a、Ar2b、Ar3、Aru is independently as defined above for αΓ5; each of d, e, f, g, h, and i is independently as defined above; j is independently as defined above for d; and k is independently Is as defined above for e; and wherein at least three of (Ar4)d(Ar5)e, (Ar6)f(Ar7)g, (ArdJArA, and (AricOjCAridkiArs, ΑΓ7, Ar9, and Ar丨1 are independent of each other) The ground is an electron-deficient aryl group, an aryl-extended vinyl group or an aryl-exetylene group and is optionally substituted. Thus, each of the at least three electron-deficient (ie, electron-transporting) moieties can be present in any one of Ar5, Ar7. Provided by Ar9 and Arn. As shown schematically in Figure 1, the compound 1 as described herein may be a discrete compound or a repeat in an oligomer or polymer (e.g., a dendrimer). Unit 10. Compound 10 includes a tertiary nitrogen-containing core portion 12 that provides a hole transport function. In some embodiments, this is a triarylamine, and in other embodiments there are two, three or more nitrogen centers. Compound 10 has three arms 14, 16 and 18. The arm may be more than three For example, 4, 5 or 6 or more. Each of the arms has an electron transport portion, which is illustrated as 2 臂 on the arm 14. In the case of the arm I4, electron transport ( That is, an electron-deficient group (Ar5)e, wherein the ΑΓ5 is electron-deficient and optionally substituted by one or more electron-withdrawing groups (these electron-donating groups provide the desired electron-deficient arm 14 also includes The transmitting portion 22, in this example, includes a base M9615.doc -37 - 201111345 - (Ar^. The electron-deficient portion 20 is close to the transmitting portion to suitably assist device efficiency. The arms 16 and 18 also include respective electron transports Portions and emitters, respectively illustrated as features 24 and 26. In each embodiment, 'for example, when any of η, p, and q is greater than 1, each of arms 14, 16 and 18 All may have a branch. 氺氺氺氺氺 Suitably, Ar, Arla, Arlb, Ar2, Ar2a, Ar2b, Ar3,
Ar3a、Ar3b、Ar3,、Ar3"、Ar4、Ar4a、Ar4b、Ar5、Ar5a、 Ar5b、Ar6、Ar6a、Ar6b、Ar7、Ar7a、Ar7b、Ar8、Ar8a、Ar3a, Ar3b, Ar3, Ar3", Ar4, Ar4a, Ar4b, Ar5, Ar5a, Ar5b, Ar6, Ar6a, Ar6b, Ar7, Ar7a, Ar7b, Ar8, Ar8a,
Ar8b、Ar9、Ar9a、Ar9b、Ar10&Ar"中之任一者或多者獨立 地經取代。適宜之取代基包括具支鏈或不具支鏈烧基、具 支鏈或不具支鏈雜烷基、具支鏈或不具支鏈烯基、具支鏈 或不具支鍵雜烯基、具支鏈或不具支鍵炔基、具支鏈或不 具支鏈雜炔基、具支鏈或不具支鏈烧氧基、芳基及雜芳基 中之一者或多者。 適宜地,若該等Ar基團經取代,則An、Arla、Arlb、Any one or more of Ar8b, Ar9, Ar9a, Ar9b, Ar10&Ar" are independently substituted. Suitable substituents include branched or unbranched alkyl, branched or unbranched heteroalkyl, branched or unbranched alkenyl, branched or unbranched heteroalkenyl, branched Or one or more of a branched alkynyl group, a branched or unbranched heteroalkynyl group, a branched or unbranched alkoxy group, an aryl group, and a heteroaryl group. Suitably, if the Ar groups are substituted, An, Arla, Arlb,
Ar2、Ar2a、Ar2b、Ar3、Ar3a、Ar3b、Ar3,、αΓ3"、Ar4、 Ar4a、Ar4b、Ar5、Ar5a、Ar5b、Ar6、Ar6a、Ar6b、Ar7、 Ar7a、Ar7b、Ar8、Ar8a、Ar8b、Ar9、Ar9a、Ar9b、An〇及Ar2, Ar2a, Ar2b, Ar3, Ar3a, Ar3b, Ar3, αΓ3", Ar4, Ar4a, Ar4b, Ar5, Ar5a, Ar5b, Ar6, Ar6a, Ar6b, Ar7, Ar7a, Ar7b, Ar8, Ar8a, Ar8b, Ar9, Ar9a, Ar9b, An〇 and
Ar〗〗中之每一者獨立地經Ci·2。烷基、Cl·20烧氧基及C5_50芳 基中之一者或多者取代’該等取代基視情況進一步經取 代。 氺氺氺氺* 149615.doc 38· 201111345 V1 C2 1 、 g 、 gj 、 g2 h hi h2 1、11、12、卜]^、1、11、15或9中之任一者 大於1 ’則相關Ar基團(例如對於a而言為Ay係針對每次出 現的彼Ar基團獨立地加以選擇。舉例而言,若&係3,貝忉 個Ar〖基團中之每一者獨立地選自其餘2個八〇基團。 同樣,舉例而言,若n大於1,則括號部分内之相關基團 (即[(Ar4)d(Ai:5)e)])係針對每次出現的n獨立地加以選擇。 因此,舉例而言,對於每次出現的6及/或11,存在不同 的電子傳輸部分係可能的。 *伞氺氺氺 適宜地’如本文所述化合物係寡聚物或聚合物。較佳 地,該化合物係樹形聚合物或樹枝狀聚合物。 ***** 較佳地,該化合物(其可為(例如)樹枝狀聚合物)之分子 里Mw在500 Da至1,〇〇〇,〇〇〇 Da範圍内,更佳為5〇〇 Da至 300,000 Da ° 氺氺氺氺氺 本發明化合物之實施例可發光,適宜地可電致發光,且 因此可用於發光裝置(例如有機電致發光裝置)中。 在又一態樣中’本發明提供包含如本文所述化合物之發 光裝置。 適宜地’有機電致發光裝置係有機發光二極體(〇LED) 或包含有機發光二極體(0LED) ^即,本文所述化合物可 用於有機發光二極體(OLED)中。 149615.doc •39- 201111345 因此’在另-態樣中,本發明提供包含如本文所述化合 物之有機電致發光裝置。 σ 在相關態樣中’本發明提供包含如本文所述化合物之有 機發光二極體(OLED)。 適宜地,如本文所述化合物可用作有機電致發光裝置之 發射層。 因此’在另-態樣中,本發明提供包含發射層之有機電 致發光裝置,其中該發射層包含如本文所述化合物。 通常’在該等有機電致發光裝置中本發明化合物係存於 有機層中。該等實施例可用於形成發射層、電荷注入層、 電荷傳輸層或電洞阻擋層中之一者或多者。通常,該層具 有薄膜形式。 因此’在另-態樣中,提供包含如本文所述化合物之薄 膜。 薄膜(例如形成發射層之薄膜)通常係含有如本文所述化 合物之薄層,該層可形成為以下量級:約^ nm至約1〇〇〇 nm厚,較佳為約丨nm至約5〇〇 nnf厚,更佳為約$⑽至約 250 nm厚’且最佳為約5 ηηι至約1〇〇 nm厚。 薄膜可含有其他組份。舉例而言,薄膜可包含主體材 料,例如導電有機化學品及如本文所述化合物。主體材料 可為(例如)聚(9-乙烯基咔唑)(ρνκ)、4,4,_N,N,_二咔唑-聯 苯(CBP)、4’4’,4M-三(N-吁唾)三苯基胺(TCTA)、N,N,_ 二苯 基-N,N,_雙(3-甲基苯基聯苯”/-工胺汀印)、N,N,_ 雙(1-萘基)-N,N,-二苯基 _;!,〗,,-聯苯 _4,4,_ 二胺(NpB)、 149615.doc 201111345 4,4',4”-參(N,N-二苯基-胺基)三苯基胺(TDATA)、1,3,5-參 (二苯基胺基)苯(TDAB)、1,3,5·參(4-(二-2-»tb啶基胺基)苯 基)*(TDAPB)、TTBND、PPD、PTDATA、BFA-1T、P-dmDPS、p-DPA-TDAB、MTBDAB、螺-mTTB、DBC、聚 (1,4-伸苯基伸乙烯基)、聚苐、聚(苯乙烯磺酸)、聚(3,4_伸 乙基二氧基嗟吩)、聚乙炔、聚"比各、聚苯胺、3 -苯基-4-(1·-萘基)-5-苯基-I,2,4-三唑(ΤΑΖ)、2-(4-聯苯)-5-(4-第三 丁基-苯基)-1,3,4-°惡二嗤(PBD)、1,3,4-°惡二唾、2,2,-(1,3-伸苯基)雙[5-[4-(1,1-二曱基乙基)苯基]](〇xd-7)或聚[2-(6-氰基-6-曱基)庚基氧基-1,4-伸苯基(CNPP)、AlOq、Each of Ar〗 independently passes Ci·2. One or more of the alkyl, Cl. 20 alkoxy groups and C5_50 aryl groups are substituted. These substituents are further substituted as appropriate.氺氺氺氺* 149615.doc 38· 201111345 V1 C2 1 , g , gj , g2 h hi h2 1,11,12, 卜]^, 1,11,15 or 9 is greater than 1 'is relevant Ar group (for example, for A, the Ay system is independently selected for each occurrence of the Ar group. For example, if & 3, each of the shells of the Ar' group is independently Selected from the remaining two gossip groups. Similarly, for example, if n is greater than 1, the relevant group in the bracket portion (ie [(Ar4)d(Ai:5)e)])) n is chosen independently. Thus, for example, for each occurrence of 6 and/or 11, it is possible to have different electron transport portions. * Umbrella 适宜 suitably 'The compounds described herein are oligomers or polymers. Preferably, the compound is a dendrimer or a dendrimer. ***** Preferably, the Mw of the compound (which may be, for example, a dendrimer) is in the range of 500 Da to 1, 〇〇〇, 〇〇〇 Da, more preferably 5 〇〇. Da to 300,000 Da ° 实施 Embodiments of the compounds of the invention can illuminate, suitably electroluminescent, and thus can be used in light-emitting devices, such as organic electroluminescent devices. In yet another aspect, the invention provides a light emitting device comprising a compound as described herein. Suitably the organic electroluminescent device is an organic light-emitting diode (〇LED) or comprises an organic light-emitting diode (OLED). That is, the compounds described herein can be used in an organic light-emitting diode (OLED). 149615.doc • 39- 201111345 Thus, in another aspect, the invention provides an organic electroluminescent device comprising a compound as described herein. σ In a related aspect The invention provides an organic light-emitting diode (OLED) comprising a compound as described herein. Suitably, the compounds as described herein are useful as emissive layers for organic electroluminescent devices. Thus, in another aspect, the invention provides an organic electroluminescent device comprising an emissive layer, wherein the emissive layer comprises a compound as described herein. Generally, the compounds of the present invention are present in the organic layer in the organic electroluminescent devices. The embodiments can be used to form one or more of an emissive layer, a charge injection layer, a charge transport layer, or a hole blocking layer. Typically, the layer has the form of a film. Thus, in another aspect, a film comprising a compound as described herein is provided. The film (e.g., the film forming the emissive layer) typically comprises a thin layer of a compound as described herein which may be formed on the order of from about ^ nm to about 1 〇〇〇 nm thick, preferably from about 丨 nm to about 5〇〇nnf is thicker, more preferably from about $(10) to about 250 nm thick' and most preferably from about 5 ηηι to about 1 〇〇 nm thick. The film may contain other components. For example, the film can comprise a host material, such as a conductive organic chemical and a compound as described herein. The host material can be, for example, poly(9-vinylcarbazole) (ρνκ), 4,4,_N,N,_dicarbazole-biphenyl (CBP), 4'4', 4M-three (N-唾 )) triphenylamine (TCTA), N, N, _ diphenyl-N, N, _ bis (3-methylphenyl biphenyl) / - amide printing), N, N, _ double (1-naphthyl)-N,N,-diphenyl_;!,〗,,-Biphenyl_4,4,_Diamine (NpB), 149615.doc 201111345 4,4',4"-parameter (N,N-diphenyl-amino)triphenylamine (TDATA), 1,3,5-gin(diphenylamino)benzene (TDAB), 1,3,5·para (4-( Di-2-»tb-pyridylamino)phenyl)*(TDAPB), TTBND, PPD, PTDATA, BFA-1T, P-dmDPS, p-DPA-TDAB, MTBDAB, spiro-mTTB, DBC, poly(1) , 4-phenyl extended vinyl), polyfluorene, poly(styrenesulfonic acid), poly(3,4_extended ethyldioxy porphin), polyacetylene, poly" ratio, polyaniline, 3 -Phenyl-4-(1·-naphthyl)-5-phenyl-I,2,4-triazole (ΤΑΖ), 2-(4-biphenyl)-5-(4-tert-butyl- Phenyl)-1,3,4-° diazepam (PBD), 1,3,4-° dihydrosodium, 2,2,-(1,3-phenylene) bis[5-[4- (1,1-dimercaptoethyl)phenyl]](〇x D-7) or poly[2-(6-cyano-6-fluorenyl)heptyloxy-1,4-phenylene (CNPP), AlOq,
Alq(Clq)2、Al(Saph-q)、Al(ODZ)3、Ph2Bq、Zn(BIZ)2、 Bepp2、Bebq2、Zn(ODZ)2、螺-PBD及 BMB-3T。 主體材料與如本文所述化合物之比率可為約1 〇 〇 : 〇 · 〇 1至 約 100:30。 另一選擇為,該薄膜可包含如本文所述化合物作為主體 材料並可進一步包含有機染料或磷光發射體,舉例而言, 染料(例如)10-(2-苯并噻唑基)-1,1,7,7-四曱基_2,3,6,7_四 鼠-1H,5H,11H-[1]苯并-η底喃并[6,7,8-ij]〇^pr|i_ii_^、3_(2- 本并塞°坐基)-7-( 一乙基胺基)-2Η-1-苯并艰u南_2_網、4-(.--氰基亞甲基)-2_第三丁基四甲基久洛尼定基 (julolidyl)-9-烯基)_4H-哌喃(DCJTB)、紅螢烯、4_(二氰基 亞曱基)-2-第二丁基_6_(對-二苯基胺基笨乙缔基)_4h_d底喃 (DCTP)、3-(二氰基亞甲基)_5,5_二曱基-^[(仁二甲基胺基) 苯乙烯基]環己烯(DCDDC)、6_甲基四曱基_ 149615.doc •41· 201111345 10-側氧基-2,3,5,6-四氫-1Η,4Η,1〇Η-11-氧雜-3a-氮雜苯并 [de]-蒽-9-基)丙烯醯基]哌喃-2,4-二酮(AAAP)、6,13-二苯 基稠五苯(DPP)及3-(N-苯基-N-對曱苯基胺基)-9-(N-對-苯 乙烯基苯基-N-對曱苯基胺基)茈[(PPA)(PSA)Pe-l]、經1,1'_ 二氰基取代之雙-苯乙烯基萘衍生物(BSN),或磷光發射 體,例如PtOEP、Ir(ppy)3或其衍生物。 如本文所述化合物與染料或磷光發射體之比率為約 100:0.01 至約 1:1。 薄膜可在適宜之基板上形成,該基板可為任一固體基 板,包括石英、玻璃、雲母、塑膠基板(例如聚對苯二曱 酸乙一醋或聚碳酸s旨)、紙、金屬或石夕。薄膜亦可層疊於 另一層上(當形成多層裝置時),或可層疊於電極上。 為形成薄膜,可將如本文所述化合物及任何額外膜組份 溶於適宜有機溶劑中。適宜之溶劑包括氣仿、曱苯、二曱 苯、苯甲酸乙酯、1,1,2,2-四氣乙烷、THF、二氣苯、均三 曱苯及上述溶劑之混合物。 可使用標準沈積或塗佈方法(包括溶液塗佈)在適宜表面 上形成薄膜。溶液塗佈包括旋塗、澆注、微凹版塗佈、凹 版塗佈、棒塗、輥塗、線棒塗佈、浸塗、喷塗、絲網印 刷、柔版印刷、平版印刷及噴墨印刷。 本文所述化合物及含有該等化合物之薄膜可用於構造 電致發光裝置(包括單居芬& 、枯早層及多層裝置)。如本文所述化合物 及含有δ玄專化合物之镇胺a 溥膜可形成有機發光二極體中之發射 層、有機薄膜電晶艚φ夕1 m Μ 體中之作用層或有機光電伏打電池中之 149615.doc •42· 201111345 作用層。該等裝置及層以及其構造已為業内所知。 一在又-態樣.中,提供-種包含陽極、陰極及如本文所述 薄膜之裝置’該薄膜係佈置於該陽極與該陰極之間。 在又-態樣中,提供裝置,其包含:陽極;佈置於該陽 極上之發射層,該發射層包含如本文所述化合物或薄膜; 及佈置於該發射層上之陰極。 在另一態樣中,提供裝置,其包含:陽極;佈置於該陽 極上之電洞傳輸層;佈置於該電洞傳輸層上之發射層;佈 置於該發射層上之電子傳輸層;及佈置於該電子傳輸層上 之陰極,其中该電洞傳輸層、該發射層及該電子傳輸層中 之至少一者包含如本文所述化合物或薄膜。 在再-態樣中,提供裝置,其包含:陽極;佈置於該陽 極上之電洞注入層;佈置於該電洞注入層上之電洞傳輸 層,佈置於邊電洞傳輸層上之發射層;佈置於該發射層上 之電子傳輸層;及佈置於該電子傳輸層上之電洞阻擋層; 佈置於忒發射層上之電子注入層;佈置於該電子注入層上 之陰極,其中邊電洞傳輸層、該發射層或該電子傳輸層中 之至少—者包含如本文所述化合物或薄膜。 在各貫施例中,本文所述化合物可用作光電伏打電池之 作用層。 在又一態樣中’本發明提供包含作用層之光電伏打電 池,其中該作用層包含如本文所述化合物或薄膜。 在各貫施例中’本文所述化合物可用作化學感測器或生 物感測器之感測層。 149615.doc •43- 201111345 在又態樣十,本發明提供包含感測層之化學或生物感 測盗’其中該感測層包含如本文所述化合物或薄膜。 適宜地,本文所提及之裝置係顯示器裝置,例如顯示器 面板。 “因此,本發明之又一態樣提供包含如本文所述化合物或 薄膜之顯示器裝置。 在又-態樣中’本發明提供製備如本文所述化合物之方 法0 在又—態樣中’本發明提供製備如本文所述裝置(例如 OLED或顯示器裝置)之方法。 在又4樣中,本發明提供如本文所述化合物在如本文 所述裝置(例如OLED或顯示器裝置)中之用途。 定義 本文所用術5吾「二芳基胺」係指三級胺基團败3,其午Alq(Clq)2, Al(Saph-q), Al(ODZ)3, Ph2Bq, Zn(BIZ)2, Bepp2, Bebq2, Zn(ODZ)2, spiro-PBD and BMB-3T. The ratio of the host material to the compound as described herein can range from about 1 〇 〇 : 〇 · 〇 1 to about 100:30. Alternatively, the film may comprise a compound as described herein as a host material and may further comprise an organic dye or phosphorescent emitter, for example, a dye such as 10-(2-benzothiazolyl)-1,1 ,7,7-tetradecyl_2,3,6,7_tetra-rat-1H,5H,11H-[1]benzo-η-deoxy[6,7,8-ij]〇^pr|i_ii_ ^,3_(2-本塞塞°坐基)-7-(ethylethylamino)-2Η-1-benzophenanthrene __ network, 4-(.--cyanomethylene) -2_T-butyltetramethyl-julolidyl-9-alkenyl)_4H-pyran (DCJTB), erythroprene, 4-(dicyanoindenyl)-2-second Base_6_(p-diphenylaminophenylethyl)_4h_d decyl (DCTP), 3-(dicyanomethylidene)_5,5-diindenyl-^[(indenylmethylamino) Styryl]cyclohexene (DCDDC), 6-methyltetradecyl _ 149615.doc •41· 201111345 10-sided oxy-2,3,5,6-tetrahydro-1 Η, 4 Η, 1 〇 Η-11-oxa-3a-azabenzo[de]-fluoren-9-yl)propenyl]pentan-2,4-dione (AAAP), 6,13-diphenyl fused pentene (DPP) and 3-(N-phenyl-N-p-phenylphenylamino)-9-(N-p-styrylphenyl-N-p-phenylphenylamino) hydrazine [(PPA) ( PS A) Pe-1], a 1,1'-dicyanyl substituted bis-styryl naphthalene derivative (BSN), or a phosphorescent emitter such as PtOEP, Ir(ppy) 3 or a derivative thereof. The ratio of compound to dye or phosphorescent emitter as described herein is from about 100:0.01 to about 1:1. The film can be formed on a suitable substrate, which can be any solid substrate, including quartz, glass, mica, plastic substrate (for example, polyethylene terephthalate or polycarbonate), paper, metal or stone eve . The film may also be laminated on another layer (when forming a multilayer device) or may be laminated to an electrode. To form a film, the compound as described herein and any additional film components can be dissolved in a suitable organic solvent. Suitable solvents include gas imitation, toluene, diphenylbenzene, ethyl benzoate, 1,1,2,2-tetraethane, THF, dioxene, mesitylene and mixtures of the above solvents. The film can be formed on a suitable surface using standard deposition or coating methods, including solution coating. Solution coating includes spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, flexographic printing, lithography, and ink jet printing. The compounds described herein and films containing such compounds are useful in the construction of electroluminescent devices (including monoprenes & early layers and multilayer devices). The compound as described herein and the cis-amine a ruthenium film containing the δ Xuan special compound can form an emission layer in the organic light-emitting diode, an organic thin film electro-crystal 艚 夕 1 1 m Μ body layer or an organic photovoltaic cell 149615.doc •42· 201111345 The working layer. Such devices and layers and their construction are known in the art. In a further aspect, a device comprising an anode, a cathode, and a film as described herein is provided. The film is disposed between the anode and the cathode. In a further aspect, a device is provided comprising: an anode; an emissive layer disposed on the anode, the emissive layer comprising a compound or film as described herein; and a cathode disposed on the emissive layer. In another aspect, a device is provided comprising: an anode; a hole transport layer disposed on the anode; an emissive layer disposed on the hole transport layer; an electron transport layer disposed on the emissive layer; A cathode disposed on the electron transport layer, wherein at least one of the hole transport layer, the emissive layer, and the electron transport layer comprises a compound or film as described herein. In a re-situation, a device is provided, comprising: an anode; a hole injection layer disposed on the anode; a hole transport layer disposed on the hole injection layer, and an emission disposed on the edge hole transport layer a layer; an electron transport layer disposed on the emissive layer; and a hole blocking layer disposed on the electron transport layer; an electron injecting layer disposed on the emissive layer; a cathode disposed on the electron injecting layer, wherein the side At least one of the hole transport layer, the emissive layer or the electron transport layer comprises a compound or film as described herein. In each of the examples, the compounds described herein can be used as a layer of a photovoltaic cell. In still another aspect, the invention provides a photovoltaic cell comprising an active layer, wherein the active layer comprises a compound or film as described herein. In various embodiments, the compounds described herein can be used as sensing layers for chemical sensors or biosensors. 149615.doc • 43- 201111345 In yet another aspect, the present invention provides a chemical or biological sensing comprising a sensing layer wherein the sensing layer comprises a compound or film as described herein. Suitably, the devices referred to herein are display devices, such as display panels. "Thus, yet another aspect of the invention provides a display device comprising a compound or film as described herein. In a further aspect, the invention provides a method of preparing a compound as described herein in a further aspect - The invention provides a method of making a device (e.g., an OLED or display device) as described herein. In yet another, the invention provides the use of a compound as described herein in a device (e.g., an OLED or display device) as described herein. As used herein, 5 "diarylamine" means a tertiary amine group which is 3, noon
每^皆獨立地為芳基或伸芳基、或以共輛方式連接U 之方基或伸《基’舉例而言’每—R可獨立地為芳基、芳 基伸烯基或芳基伸块基。共㈣接體基團之較佳實例係伸 乙,基及伸块基:使得R為芳基/伸芳基伸乙婦基或芳基乂 伸方基伸乙快基。在三芳基胺位於如本文所述化合物之核 心部:t之背景下’胺取代基”之至少一者係二齒的(例 如伸方基)以允許連接至f部分。因&,上文對芳基之論 述適用於相應之伸芳基。 ™ 本文所用術語「芳基」係指自芳香族化合物藉由去除— 個氫原子所得到之單價芳香族基團。芳香族化合物係具有 I49615.doc -44 - 201111345 4n+2 —電子之環狀化合物 叙。y·々一 > 诉寻於或大於〇之整 數。在各貫施例中,芳基可具有5個至咖個環原子^ 5個至80個、更佳5個至5〇個 “ 乂土 文佳5個至3 〇個且最佳 個環原子。處於取代基背景下 最佳5個至 予以陳述。 <方基之貫例將在下文中 本文所用術語「伸芳基」係指自芳香 兩個氯原子所得到之二價芳香族基團。芳香族化= 有㈣個π電子之環狀化合物’其中η係等於或大於。之整 數。在各實施例中,伸芳基可具有5個至⑽個環原子,較 請謂個、更佳5個至洲、更佳5個㈣個且最佳⑽ 至20個環原子。處於取代基背景下之伸m例將在下 文中予以陳述。 本文所用術語「雜芳基」係指其中一個或多個骨架碳原 子已由雜原子(例如N、0、s、Si或P中之一者或多者)代替 之芳基。 本文所用術語「雜伸芳基」係指其中—個或多個骨架碳 原子已由雜原子(例如N、〇、s、Si*p中之一者或多者)代 替之伸芳基。 本文所用符號「Ar」ϋ常係指芳基、伸芳基、雜芳基、 雜伸芳基、芳基及毗鄰伸乙烯基(「芳基伸乙烯基」)、伸 芳基及毗鄰伸乙烯基(「伸芳基伸乙烯基」)、雜芳基及毗 鄰伸乙烯基(「雜芳基伸乙烯基」)、雜伸芳基及毗鄰伸乙 稀基(雜伸芳基伸乙坤基」)、芳基及Β比鄰伸乙炔基(「芳 基伸乙炔基」)、伸芳基及毗鄰伸乙炔基(「伸芳基伸乙炔 149615.doc -45- 201111345 基」)、雜芳基及毗鄰伸乙炔基(「雜芳基伸乙炔基」)、或 雜伸芳基及毗鄰伸乙炔基(「雜伸芳基伸乙炔基二或二 基或伸芳基及毗鄰氮或胺基團(「胺基芳基」《「胺基伸 ^」)。如上文所說明,術語「芳基」包括雜芳二 二整起見雜芳基已在上文列表中列舉出。其同樣適用於 u雜伸芳基、雜伸芳基伸乙烯基及雜伸芳基伸乙炔 基。 、 應瞭解,若特定域_述為包括㈣基或雜伸芳基, 但若,一伸芳基或雜伸芳基出現在分子末端且為單價^ 該特疋基團將為芳基或雜若美 ^ a 土㈣方基同樣’應瞭解,若特定七 基團闡述為包括芳基戍雜芳美 ^八工 $ 土次雜方基但若此一芳基或雜芳基出 現在分子内且為二價,則 基。 !°亥特疋基團將為伸芳基或雜伸芳 伸乙埽基」係mCH=CH_代表之 伸乙炔基」係指由(Csc_代表之 本文所用術語 價基團。 本文所用術語 基團。 .....一」^日田A -CSC-代表之二價 本文所用術語「胺基芳基 「 連接至芳mi 」及⑯基伸芳基」通常係指 N(R) A 土 3方土之胺基團。例如,-Ar-N(R)2或-A卜 N(R)-Ar_,其中R係胺取代基。 本文所用術語「聚(芳基 胺美圍^ 女)」係才曰至少兩個毗鄰之芳基 胺基團。適宜地’該等芳 中出現聚(芳㈣之背景下,其將適宜地為單齒或二齒 149615.docEach of the groups is independently an aryl group or an aryl group, or a group of U groups connected to a common mode or a "base", for example, 'each-R can independently be an aryl group, an arylalkylene group or an aryl group. base. A preferred example of the co-(iv) linker group is a B, a group and a stretch block: such that R is an aryl/arylene group or an aryl group. At least one of the 'amine substituents' in the context of a triarylamine located in the core of a compound as described herein: t is dentate (e.g., a stretch group) to allow attachment to the moiety f. & The discussion of aryl groups applies to the corresponding extended aryl groups.TM The term "aryl" as used herein refers to a monovalent aromatic group derived from an aromatic compound by removal of one hydrogen atom. The aromatic compound has a ring compound of I49615.doc -44 - 201111345 4n+2 - electron. y·々一 > The appeal is greater than or equal to the integer of 〇. In each of the examples, the aryl group may have 5 to 80 ring atoms, preferably 5 to 80, more preferably 5 to 5 “ "5 to 3 乂 of the 乂土文佳 and the best ring atom In the context of a substituent, the best five are stated. <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Aromaticization = a cyclic compound having (four) π electrons where η is equal to or greater than. The whole number. In various embodiments, the extended aryl group may have from 5 to (10) ring atoms, more preferably 5, more preferably 5 (four) and most preferably (10) to 20 ring atoms. An example of stretching in the context of a substituent will be set forth below. The term "heteroaryl" as used herein, refers to an aryl group in which one or more of the backbone carbon atoms have been replaced by a heteroatom (e.g., one or more of N, 0, s, Si, or P). The term "heteroaryl" as used herein, refers to an extended aryl group wherein one or more of the backbone carbon atoms have been replaced by a heteroatom (e.g., one or more of N, 〇, s, Si*p). The symbol "Ar" as used herein generally refers to aryl, aryl, heteroaryl, heteroaryl, aryl and adjacent vinyl ("aryl extended vinyl"), extended aryl and adjacent vinyl. ("Extremely extending vinyl"), heteroaryl and adjacent vinyl ("heteroaryl"), heteroaryl and adjacent ethylene (heteroaryl) And anthracene ethynyl ("aryl ethynyl"), aryl and ethynyl ("aryl acetylene 149615.doc -45- 201111345"), heteroaryl and adjacent ethynyl ( "heteroaryl ethynyl"), or a heteroaryl group and an adjacent ethynyl group ("heteroaryl group ethynyl bis or diyl or aryl group and adjacent nitrogen or amine group ("amino aryl"" "Amine-based extension". As explained above, the term "aryl", including heteroaryldidentate heteroaryl, is listed above in the list. It is equally applicable to u-heteroaryl, hetero-aromatic a base-stretching vinyl group and a hetero-aryl group ethynyl group. It should be understood that if a specific domain is described as including a (tetra) group or a hetero-aryl group, If an aryl or heteroaryl group is present at the end of the molecule and is a monovalent group, the thiol group will be an aryl group or a heterogeneous group, and the same will be understood if a specific seven group is included. Aryl 戍 芳 ^ ^ 八 ^ ^ 土 土 土 土 土 土 土 土 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但" Extension ethynyl group" is a term valent group as used herein (Csc_. The term group used herein. ..... a" ^ Hita A-CSC - Represented bivalent The term "aminoaryl" "attached to aryl mi" and 16 aryl extended aryl" as used herein generally refers to the amine group of the N(R) A earth 3 earth. For example, -Ar-N(R 2 or -Ab N(R)-Ar_, wherein R is an amine substituent. The term "poly(arylamine mei)" is used herein to mean at least two adjacent arylamine groups. In the context of the presence of poly (aryl), it will suitably be monodentate or bidentate 149615.doc
-46- 201111345 本文所用術語「烧基」係指具有i個至2g個碳原子之具 支鍵或不具支鏈單價烴基團。同樣,本文所用「伸烧基= 基團係指具有丨個至卿碳原子之具支鏈或不具支鍵二價 =團:應理解,稀基及伸稀基係含有—個或多個雙鍵之 早<貝及:價烴基團之相應術語且炔基及伸炔基係含有一個 或夕個一鍵之單價及一價烴基團之相應術語。 本文所用術語「破、「磁其 「 山^ J厌基」、烴」及「烴基」係指僅 具有碳及氫原子之化合^j B / + w m σ物及/或基團(但下文參見「碳 環」)。 本文所用術語「雜係指具有 井虿至少一個雜原子之化合物 及/或基團’例如’諸如硼、矽、 〉 虱、破、氧、硫及硒(更 通*為氮、氧及硫)等多價雜原子( 卞(其亦適宜作為環雜原子) 及诸如氟、氯、溴及碘等單價雜原子。 本文所用術語「飽和俜指 具有任何碳_碳雙鍵或碳- 石反二鍵之化合物及/或基團。 本文所用術語「不飽和」係指且 ,、有至 >、一個碳-碳雙鍵 或石厌-奴二鍵之化合物及/或基團。 化δ物及/或基團可部分 不飽和或完全不飽和。 本文所用術語「單齒取代基 之取代基。 」料具有一個共價連接點 本文所用術語「單價單齒取代基 _ 」係h具有一個共價連 接點且經由單鍵連接之取代基。 、 .该孝取代基之實例包括函 基、羥基及烷基。 @ 本文所用術語「二齒取代基」 '、心具有兩個共價連接點 149615.doc •47· 201111345 且在兩個其他部分之間奋告电 兄田連接基團之取代基。該等取代 基之實例包括伸烷基及伸芳基。 本文所用術語「缺電子」係指價電子缺乏而使得兀系統 (例如芳基)對其所連接之基團適宜地展示拉電子作用之兀系 統。即’其具有將電子自其所連接之基團拉離之傾向。 缺電子芳基之實例包括㈣基、㈣基、㉝二唾基及三 。坐基及其相應之伸芳基結構。 拉電子芳基可自相鄰芳基拉電子之能力往往使拉電子芳 基比不拉電子之相鄰芳基更加電子緻密(類似於叫導體中 所用之η型材料),且因此傳輸電子能力更強。通常,拉電 子基團係可產生毗鄰骨架之正或5_正區域以將電子從骨架 拉向取代基的基團。 較佳地,缺電子π系統具有一個或多個與其連接之拉電 子取代基。實際上’該基團之電子缺失可能係因存在拉電 子取代基而引起。因此’在Ar6之情形Τ,芳基或伸芳基兀 系統(例如)因所連接之拉電子基團而係缺電子的。 拉電子基團之實例包括-CN、-COOH、南基(尤其_F 及-Cl)、-N〇2、-CO、全氟烷基、銨基、亞硫醯基、磺醯 基、經由氧連接之醯胺基、吡啶鏽、鱗、吡啶基、噻唑 基、噁二唑基及三唑基。 官能基團相對於氫可方便地分為「拉電子」(_δ)或「供 電子」( + δ)基團。供電子基團之實例包括(但不限於)(按強 度增加之大致順序)-0·、-COO·、-CR3、-CHR2、-CH2R、 -CH3及-D。拉電子基團之實例包括(但不限於)(按強度減小 149615.doc -48· 201111345 之大致順序)-NR3+、-SR2+、-NH3"1"、-N〇2、_S〇2r_、 -CN、-S〇2Ar、-COOH、-F、-Cl、-Br、-I、-〇Ar、 -COOR、-OR、-COR、-SH、-SR、-OH、-Ar及-CH=CR2 (其中Ar表示芳基)。參見(例如)Ceppi等人,1973, Tetrahedron Letters,第 3627 頁。 取代基 本文所用片語「視情況經取代」係指可未經取代或可經 取代之母體基團。 除非另有說明,否則本文所用術語「經取代」係指具有 一個或多個取代基之母體基團》術語「取代基」在本文中 係以習用含義使用且係指以共價方式連接至或(若適當)稠 合至母體基團之化學部分。多種取代基已為業内所熟知, 且其形成及引入各種母體基團中之方法亦已為業内所熟 知。 取代基之實例將在下文中予以更詳細闡述。 烧基:如上文所說明,本文所用術語「燒基」係指藉由 自具有1個至20個碳原子(除非另有說明)之烴化合物的碳原 子去除-個氫原子而獲得的單價部分,其可為脂肪族或脂 環族,且其可為飽和或不飽和(例如,部分不飽和、完全 因此,術語「烧基」包括下文所論述之子類稀 基、炔基、環烷基、環烯基、環炔基等。 在烷基之背景下,下標(例如, Γ 笪、志-山 K4 、C丨-20、c2-7、 3-7專)表不奴原子之數量或碳原子 一士 -V〜 致里犯圍。舉例而 吕,本文所用術語「C“4烷基 竿U而 私具有1個至4個碳原子 149615.doc -49· 201111345 之烷基。烷基之群之實例包括Ci 4烷基(「低碳數烷 基」)、Cw烷基及c,·^烷基。注意:第一下標可隨其他限 制條件有所變化;舉例而言,對於不飽和烷基而言,第一 下標必須至少為2 ;對於環狀及具支鏈烷基而言,第一下 標必須至少為3 ;等。 (未經取代)飽和烷基之實例包括(但不限於)曱基(c〇、乙 基(c2)、丙基(c3)、丁基(C4)、戊基(C5)、己基(c6)、庚基 (C7)、辛基(C8)、壬基(c9)、癸基(Ci〇)、十一烷基(Ch)、 十一烧基(C丨2)、十二烧基(Cu)、十四院基(Cw)、十五烧基 (c15)、十六烷基(c16)、十八烷基(Ci8)及二十烷基(c2〇)。 (未經取代)飽和直鏈烷基之實例包括(但不限於)甲基 (C丨)、乙基(c2)、正丙基(c3)、正丁基(c4)、正戊基 pentyl,n-amyl)(C5)、正己基(C6)、及正庚基(c7)、正辛基 (c8)、正癸基(Cl0)、正十二烷基(c.正十四烷基(C14)、 正十六烷基(Cd、正十八烷基(Cu)、及正二十烷基(c2〇)。 (未經取代)飽和具支鏈烷基之實例包括異丙基(c3)、異 丁基(c〇、第二丁基(C:4)、第三丁基(c4)、3戊基、異戊基 (C5)、3-曱基丁基、及新戊基(C5)、33二曱基丁基、2_乙 基丁基、4_甲基戊基、2·己基、2-庚基、2-辛基、2-乙基 己基、3’7-一曱基辛基、2_ 丁基辛基、2_己基癸基、辛 基十二烧基。 烯基.如上文所說明,本文所用術語「烯基」係指具有 一個或多個碳-碳雙鍵之烧基。稀基之群之實例包括C24烯 基、C2_7浠基、C2.2Q稀基。 149615.doc •50· 201111345 (未經取代)不飽和烯基之實例包括(但不限於)乙烯基 (ethenyl3vinyl)(-CH=CH2) ^ 1 ^ ^ & (-CH=CH-CH3) ^ 2-^ 烯基(烯丙基,-CH-CH=CH2)、異丙烯基(1_甲基乙烯基, -c(ch3)=ch2)、丁烯基(c4)、戊烯基(c5)及己稀基(c/ 炔基:如上文所說明’本文所用術語「块基」係指具有 -個或多個碳·碳三鍵之烧基。块基之群之實例包括^块 基、C2-7快基、C2-2G快基。 (未經取代)不飽和炔基之實例包括(但不限於)乙炔基 (ethynyl,ethinyl)(-〇CH)及 2_ 丙炔基(炔丙基,_ci^· C三CH)。 環烧基:本文所用術語「環院基」係指亦為環基之烧 基;即,藉由自碳環化合物之碳環之脂環族環原子去除一 個氫原子而獲得的單價部分’該碳環可為飽和或不飽和 (例如,部分不鮮、完全不飽和),該部分具有3個至2〇個 碳原子(除非另有說明),包括3個至2〇個環原子。因此,術 語「環烷基」包括子類環烯基及環炔基。較佳地,每一環 皆具有3個^7個環原子。環烧基之群之實例包括^環炫 基、C3_i5環烷基、C3_1Q環烷基、c3_7環烷基。 環烷基之實例包括(但不限於)彼等衍生自下列者·· 飽和單環烴化合物: 環丙烧(C3)、環τ烧(c4)、環戊烧(c5)、環己燒(c6)、環庚 烧(C7)、甲基環丙烧(c4)、二甲基環丙烧(c5)、甲基環丁烧 (C5)、二甲基環丁燒(C6)'甲基環戊烧(c6)、:甲基環戍炫 (⑸、曱基環己烧㈣、二甲基環己烧(Cs)、薄荷烧 149615.doc -51- 201111345 不飽和單環烴化合物: 環丙烯(C3)、環丁烯(C4)、環戊烯(C5)、環己烯(c6)、甲基 環丙烯(C4)、二甲基環丙烯(C5)、甲基環丁烯(c5)、二甲基 環丁烯(C:6)、甲基環戊烯(C6)、二甲基環戊烯(c7)、曱基環 己烯(C7)、二甲基環己烯(c8); 飽和多環煙化合物: 側柏烷(c10)、f烷(Ci〇)、蒎烷(Ci〇)、莰烷(Ci〇)、降蒈烷 (C7)、降蒎烷(C7)、降莰烷(C7)、金剛烷(CiG)、萘烷(十氫 化萘)(C10); 不飽和多環烴化合物: 莰烯(c1())、檸檬烯(CiQ)、蒎烯(Ci〇); 具有芳香族環之多環烴化合物: 茚(c9)、二氫茚(例如,2,夂二氫_1H•茚)(c9)、四氫化萘 (1,2’3,4-四氫萘)(Ci〇)、二氫苊(c12)、第(C丨3)、非那烯 (C13)、醋菲(c15)、醋蒽(Cl6)、膽蒽(C20)。 亞烷基:本文所用術語「亞烷基」係指藉由自具有丄個 至20個碳原子(除非另有說明)之烴化合物之脂肪族或脂環 族碳原子去除兩個氫原子而獲得的二價單齒部分。亞烷基 之群之實例包括c丨心亞烷基、Ci 7亞烷基、C14亞烷基。 亞烷基之實例包括(但不限於)亞曱基(=CH2;)、亞乙美 (=ch-ch3)、亞乙烯基(=C=CH2)、亞異丙基(=c(c叫)2): 亞環戊基及亞苄基(=CH-Ph)。 次烧基:本文所用術語「次烧基」係指藉由自具有心 至20個碳原子(除非另有說明)之烴化合物之脂肪族或脂環 149615.doc •52· 201111345 族碳原子去除三個氫原 之群之實例包括基;;貝早齒部分。次烧基 次燒基之實例包括(作不:二?基、Cl挪 .柯韻叔衫基把(ph—)不限於)〇基㈣)' 次乙基 碳環基:本文卢斤田i . . 斤用術语「碳環基」係指麩ώ ώ 物之環原子去除— 乎、才曰藉由自碳環化合 有3個至20個環原子(除 早 <貝4刀,該部分具 有3個至7個環原子。 說明)。較佳地,每一環皆具 在此背景下,下標(例如,、c 子之數量戋環;^ 杏 3 7 5·6等)表示環原 m原子之數量範圍。舉例 「c5-6碳環基」係指|〇 5 本文所用術語 如具有5個或6個環原子之#卢# m 土之群之實例包括c3,2。碳環基、c。。碳产:衣土。敌核 基、Cp碳環基及C57碳環基。 衣土、C:5-丨0碳環 碳環基團之實例包括(但不限於)彼等 述者^彼等下文作為碳芳基閣述者。為環院基閣 雜衣基.本文所用術語「雜環基 物之環原子去除“错由自雜環化合 双项千而獲得的單僧八 有3個至20個環原子(除非另有說明),。y以分具 雜原子。較佳地,每_ 、個至〗〇個係環 個至4個係環雜原子。 個%原子,其t j 在此背景下,下標⑽如, 子(碳原子或雜原s 3·7、C5.6等)表示環 …… 環原子之數量範圍。舉例而 5本文所用術語「c56雜環 牛句而 子之雜ja I '、曰/、有5個或6個淨@ 子之㈣基。雜環基之群之實例包 及原 2〇雜%基、C5-20雜 149615.doc -53- 201111345 ΓΓ·|5雜環基、%雜環基、‘雜環基、C512雜環 =雜芳基之雜環基之實例與芳基—起闡述於下文中。 自如上文所說明’本文所用術語「芳基」係指藉由 =物之芳香環原子去除—個氫原子而獲得 明),地,每-環=:=_有說 一丄 )之數里或環原子之數量範圍。舉例而 文所用術語「C5_6芳基」係指具有5個或6個環原子 4 芳f之群之實例包括一芳基、。5.15芳基、c5.12 方1 C51。方I、C5·7芳S、C5·6芳基、C5芳基及c6芳基。 玉衣原子可為如「破关其 反方基」中之所有碳原子。碳芳基之實 :包括C5,碳芳基、c-碳芳基、“碳芳基、CW炭芳 二C5.10石反方基、C5·7碳芳基、C5-6碳芳基、C5碳芳基及C6 碳芳基。 山芳土之貫例包括(但不限於)彼等衍生自苯(即,苯 基)(C6)奈(Cl。)、奠(Cl°)、蒽(c14)、菲(c14)、稠四苯 (Cu)及芘(c16)者。 包3铜玉衣(其中至少—者係芳香族環)之芳基之實例包括 (C不限於)何生自二氮節(例如,二氮·出·節)(C9)、節 (C9)、異節(C9)、四氫化萘(1,2,3,4•四氫蔡(〜)、二氫危 (C〗2)第(C丨3)、非那烯(C丨3)、醋菲(Ci5)及醋慕(Ci6)之基 149615.doc -54- 201111345 團。 另一選擇為,環原子可包括一個或多個如「雜芳基」中 之雜原子。雜方基之實例包括C5-1QQ雜芳基、C5_2〇雜芳 基、C5·丨5雜芳基、Cs-丨2雜芳基、Cs.io雜芳基、C5.7雜芳 基、c5_6雜芳基、(:5雜芳基及c6雜芳基。 單環雜^•基之實例包括(但不限於)彼等衍生自下列者. N]:吡咯(唑)(c5)、吡啶(嗪)(C6); 〇1 : °夫喃(氧雜環戊二稀)(c5); S!:噻吩(硫茂)(c5); Νθ〗:噁唑(C5)、異噁唑(C5)、異噁嗪(c6); Ν2〇ι : °惡二嗤(咬咕)(c5); Ν3〇ι :噁三唑(c5);-46- 201111345 The term "alkyl" as used herein refers to a branched or unbranched monovalent hydrocarbon group having from i to 2g carbon atoms. Similarly, as used herein, "extension base = group refers to a branched or unbranched divalent group having one to two carbon atoms = group: it should be understood that a thin base and a thin base contain one or more double The early term of the bond <Bei and: the corresponding term of the valence hydrocarbon group and the alkynyl and alkynyl groups contain one or a single bond of the monovalent and monovalent hydrocarbon groups. The term "broken, magnetic" The term "hydrocarbon", "hydrocarbon" and "hydrocarbyl" refer to a compound having only carbon and hydrogen atoms and/or a group (but see "carbocycle" hereinafter). The term "hetero" as used herein refers to a compound and/or group having at least one heteroatom of a well such as, for example, boron, ruthenium, osmium, ruthenium, oxygen, sulfur, and selenium (more readily being nitrogen, oxygen, and sulfur). Multivalent heteroatoms (卞 (which is also suitable as a ring heteroatom) and monovalent heteroatoms such as fluorine, chlorine, bromine and iodine. The term "saturated 俜" as used herein has any carbon-carbon double bond or carbon-stone anti-two. The compound and/or group of the bond. The term "unsaturated" as used herein means a compound and/or a group of a carbon-carbon double bond or a stone-nano bond. And/or the group may be partially unsaturated or completely unsaturated. The term "substituent substituent of a monodentate substituent" as used herein. The material has a covalent attachment point. The term "monovalent monodentate substituent" as used herein has a total a valency point of attachment and a substituent attached via a single bond. Examples of the filbert substituent include a group, a hydroxy group, and an alkyl group. @ The term "dentate substituent" is used herein, and the heart has two covalent attachment points 149615 .doc •47· 201111345 and in two other parts Examples of such substituents include alkyl and aryl groups. The term "electron deficiency" as used herein refers to a lack of valence electrons such that a ruthenium system (eg, an aryl group) The group to which it is attached suitably exhibits a enthalpy system for pulling electrons. That is, it has a tendency to pull electrons away from the group to which it is attached. Examples of electron-deficient aryl groups include (tetra), (d), and 33 dips. The base and the corresponding aryl structure. The ability of the pull electron aryl group to pull electrons from adjacent aryl groups tends to make the electron aryl group more electronically dense than the adjacent aryl group of the electron. It is called the n-type material used in the conductor, and thus the electron transporting ability is stronger. Usually, the electron withdrawing group can generate a positive or a positive region adjacent to the skeleton to pull electrons from the skeleton to the substituent. Preferably, the electron-deficient π system has one or more pull-electron substituents attached thereto. In fact, the electron deletion of the group may be caused by the presence of a pull-electron substituent. Therefore, in the case of Ar6, an aryl group Or extended aryl system ( For example, electron-deficient groups are electron-deficient. Examples of electron-withdrawing groups include -CN, -COOH, South base (especially _F and -Cl), -N〇2, -CO, perfluoro An alkyl group, an ammonium group, a sulfinyl group, a sulfonyl group, an amide group linked via an oxygen, a pyridine rust, a scaly, a pyridyl group, a thiazolyl group, an oxadiazolyl group, and a triazolyl group. The functional group is relative to hydrogen. Conveniently divided into "pull electron" (_δ) or "electron supply" (+ δ) groups. Examples of electron donating groups include (but are not limited to) (in the approximate order of increasing strength) -0, -COO· , -CR3, -CHR2, -CH2R, -CH3, and -D. Examples of electron withdrawing groups include, but are not limited to, (in the approximate order of strength reduction 149615.doc -48·201111345) -NR3+, -SR2+, -NH3"1", -N〇2, _S〇2r_, -CN, -S〇2Ar, -COOH, -F, -Cl, -Br, -I, -〇Ar, -COOR, -OR, -COR , -SH, -SR, -OH, -Ar and -CH=CR2 (wherein Ar represents an aryl group). See, for example, Ceppi et al., 1973, Tetrahedron Letters, p. 3627. Substituents The phrase "optionally substituted" as used herein refers to a parent group which may be unsubstituted or substituted. The term "substituted" as used herein, unless otherwise indicated, refers to a parent group having one or more substituents. The term "substituent" is used herein in the ordinary sense and refers to a covalently attached or (if appropriate) fused to the chemical moiety of the parent group. A wide variety of substituents are well known in the art, and methods for their formation and introduction into various parent groups are also well known in the art. Examples of substituents will be explained in more detail below. Alkyl group: As explained above, the term "alkyl group" as used herein refers to a monovalent moiety obtained by removing a hydrogen atom from a carbon atom of a hydrocarbon compound having from 1 to 20 carbon atoms (unless otherwise stated). , which may be aliphatic or alicyclic, and which may be saturated or unsaturated (eg, partially unsaturated, completely, therefore, the term "alkyl" includes sub-types, alkynyl, cycloalkyl, a cycloalkenyl group, a cycloalkynyl group, etc. In the context of an alkyl group, the subscripts (for example, Γ 笪, 志-山 K4, C丨-20, c2-7, 3-7) indicate the number of slave atoms or For example, the term "C" 4 alkyl 竿U and 1 to 4 carbon atoms 149615.doc -49· 201111345 alkyl. Examples of such groups include Ci 4 alkyl ("lower alkyl"), Cw alkyl, and c, alkyl. Note: The first subscript may vary with other constraints; for example, For unsaturated alkyl groups, the first subscript must be at least 2; for cyclic and branched alkyl groups, the first subscript must be at least 3; Examples of (unsubstituted) saturated alkyl groups include, but are not limited to, mercapto groups (c〇, ethyl (c2), propyl (c3), butyl (C4), pentyl (C5), hexyl (c6) , heptyl (C7), octyl (C8), fluorenyl (c9), fluorenyl (Ci), undecyl (Ch), eleven (C丨2), twelve alkyl (Cu) ), fourteen yards (Cw), fifteen (c15), cetyl (c16), octadecyl (Ci8) and eicosyl (c2). (unsubstituted) saturated straight Examples of alkenyl groups include, but are not limited to, methyl (C丨), ethyl (c2), n-propyl (c3), n-butyl (c4), n-pentyl pentyl, n-amyl (C5) , n-hexyl (C6), and n-heptyl (c7), n-octyl (c8), n-decyl (Cl0), n-dodecyl (c. n-tetradecyl (C14), n-hexadecane Base (Cd, n-octadecyl (Cu), and n-icosyl (c2). Examples of (unsubstituted) saturated branched alkyl groups include isopropyl (c3), isobutyl (c 〇, second butyl (C: 4), tert-butyl (c4), 3 pentyl, isopentyl (C5), 3-mercaptobutyl, and neopentyl (C5), 33 decyl Butyl, 2-ethylbutyl 4-methylpentyl, 2·hexyl, 2-heptyl, 2-octyl, 2-ethylhexyl, 3'7-monodecyloctyl, 2-butyloctyl, 2-hexyldecyl, octyl Alkenyl. Alkenyl. As explained above, the term "alkenyl" as used herein refers to a burnt group having one or more carbon-carbon double bonds. Examples of groups of dilute groups include C24 alkenyl, C2_7浠Base, C2.2Q dilute. 149615.doc •50· 201111345 (unsubstituted) Examples of unsaturated alkenyl groups include, but are not limited to, ethenyl3vinyl (-CH=CH2) ^ 1 ^ ^ & -CH=CH-CH3) ^ 2-^ alkenyl (allyl, -CH-CH=CH2), isopropenyl (1-methylvinyl, -c(ch3)=ch2), butenyl ( C4), pentenyl (c5) and hexyl (c/alkynyl: as used hereinabove, the term "block group" as used herein refers to a group having one or more carbon-carbon triple bonds. Examples of the group of block bases include a block base, a C2-7 fast base, and a C2-2G fast base. Examples of (unsubstituted) unsaturated alkynyl groups include, but are not limited to, ethynyl, ethinyl (-〇CH) and 2-propynyl (propargyl, _ci^·C tri CH). Cycloalkyl: The term "ring-based" as used herein refers to a base which is also a ring group; that is, a monovalent moiety obtained by removing one hydrogen atom from an alicyclic ring atom of a carbocyclic compound. The carbocyclic ring can be saturated or unsaturated (e.g., partially non-fresh, fully unsaturated) having from 3 to 2 carbon atoms (unless otherwise stated), including from 3 to 2 ring atoms. Thus, the term "cycloalkyl" includes sub-type cycloalkenyl and cycloalkynyl. Preferably, each ring has 3 ^ 7 ring atoms. Examples of the group of the cycloalkyl group include a cyclohexyl group, a C3_i5 cycloalkyl group, a C3_1Q cycloalkyl group, and a c3-7 cycloalkyl group. Examples of cycloalkyl groups include, but are not limited to, those derived from the following: saturated monocyclic hydrocarbon compounds: cyclopropane (C3), cyclopropene (c4), cyclopentane (c5), cyclohexane ( C6), cycloheptane (C7), methylcyclopropane (c4), dimethylcyclopropane (c5), methylcyclobutane (C5), dimethylcyclobutane (C6)'methyl Cyclopentene (c6), methyl oxime (5), fluorenylcyclohexane (tetra), dimethylcyclohexane (Cs), mint 149615.doc -51- 201111345 unsaturated monocyclic hydrocarbon compound: ring Propylene (C3), cyclobutene (C4), cyclopentene (C5), cyclohexene (c6), methylcyclopropene (C4), dimethylcyclopropene (C5), methylcyclobutene (c5) ), dimethylcyclobutene (C:6), methylcyclopentene (C6), dimethylcyclopentene (c7), nonylcyclohexene (C7), dimethylcyclohexene (c8) Saturated polycyclic compounds: flavonoids (c10), f alkane (Ci〇), decane (Ci〇), decane (Ci〇), norbornane (C7), norbornane (C7), Decalin (C7), adamantane (CiG), decalin (decalin) (C10); unsaturated polycyclic hydrocarbon compound: terpene (c1()), limonene (CiQ) ), a terpene (Ci〇); a polycyclic hydrocarbon compound having an aromatic ring: 茚(c9), indoline (for example, 2, oximehydro-1H•茚) (c9), tetrahydronaphthalene (1, 2'3,4-tetrahydronaphthalene) (Ci〇), indoline (c12), (C丨3), phenalenol (C13), phenanthrene (c15), vinegar (Cl6), cholesteric (C20). Alkylene: As used herein, the term "alkylene" refers to the removal of two by aliphatic or alicyclic carbon atoms from a hydrocarbon compound having from one to twenty carbon atoms (unless otherwise stated). A divalent monodentate moiety obtained by a hydrogen atom. Examples of the group of alkylene groups include c 丨 cardinyl, Ci 7 alkylene, C 14 alkylene. Examples of alkylene include, but are not limited to, Aa Base (=CH2;), acetonitrile (=ch-ch3), vinylidene (=C=CH2), isopropylidene (=c(c)2): cyclopentylene and benzylidene ( =CH-Ph). Sub-alkyl: The term "sub-alkyl" as used herein refers to an aliphatic or alicyclic ring of a hydrocarbon compound having a core to 20 carbon atoms (unless otherwise stated) 149615.doc •52 · 201111345 Examples of a group of carbon atoms removing three hydrogenogens including a base; Examples of sub-sintering bases include (do not: di-base, Cl to move. Ke Yunshu shirt base (ph-) is not limited to) sulfhydryl (four)) 'ethylidene carbocyclyl: this article Lu Jintian i. The term "carbocyclyl" is used to mean the removal of the ring atom of the bran — — — 曰 曰 曰 曰 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 ( ( ( ( ( ( ( ( ( ( ( ( Up to 7 ring atoms. Description). Preferably, each ring has a subscript (e.g., the number of c sub-rings; ^ april 3 7 5·6, etc.) indicates the range of the number of m atoms of the ring. For example, "c5-6 carbocyclyl" means |〇 5 The terminology used herein, such as a group of 5 or 6 ring atoms, is an example of c3,2. Carbocyclic group, c. . Carbon production: clothing soil. Dinucleotide group, Cp carbocyclic group and C57 carbocyclic group. Examples of soil, C:5-丨0 carbocyclic carbocyclic groups include, but are not limited to, those of the above, as those of the carbon aryl group. The term "ring atom removal of a heterocyclic substrate" as used herein. "The substituent obtained from the heterocyclic compound is a three-to-one ring having three to twenty ring atoms (unless otherwise stated). ),. y is divided into heteroatoms. Preferably, each _, each to 〇 系 ring to 4 ring hetero atoms. % atom, its t j In this context, the subscript (10) such as, sub (carbon atom or heterogene s 3 · 7, C5.6, etc.) represents the ring ... the number of ring atoms. For example, 5 the term "c56 heterocyclic bovine sentence and heterozygous ja I ', 曰 /, has 5 or 6 net @子之(四) groups. Example group of heterocyclic group and original 2% Illustrative examples of heterocyclic groups of heterocyclic groups, heterocyclic groups, heterocyclic groups of heterocyclic groups, heterocyclic groups, heterocyclic groups, heterocyclic groups of heterocyclic groups, and aryl groups In the following, as the above description, the term "aryl" as used herein refers to the removal of - a hydrogen atom by the aromatic ring atom of the substance, and the ground, per-ring =:=_ has a glimpse The number of or the number of ring atoms. The term "C5_6 aryl" as used herein, as used herein, refers to an example of a group having 5 or 6 ring atoms 4 aryl f including an aryl group. 5.15 aryl, c5.12 square 1 C51. Formula I, C5·7 aryl S, C5·6 aryl, C5 aryl and c6 aryl. The jade atom can be all carbon atoms in the "breaking the anti-square". Carbon aryl group: including C5, carbon aryl, c-carbon aryl, "carbon aryl, CW carbon aryl C5.10 stone anti-group, C5 · 7 carbon aryl, C5-6 carbon aryl, C5 Carbon aryl and C6 carbon aryl. Examples of smectite include, but are not limited to, those derived from benzene (ie, phenyl) (C6) na (Cl.), (Cl°), 蒽 (c14). ), phenanthrene (c14), fused tetraphenyl (Cu), and ruthenium (c16). Examples of the aryl group of the package 3 copper jade (at least - the aromatic ring) include (C is not limited to) Nitrogen nodules (for example, dinitrogen and rhodium) (C9), nodules (C9), heteronuclear (C9), tetrahydronaphthalene (1,2,3,4•tetrahydrocai (~), dihydrogen ( C〗 2) The basis of the (C丨3), phenazoline (C丨3), acetophene (Ci5) and vinegar (Ci6) 149615.doc -54- 201111345 group. Another option is that the ring atom can Including one or more heteroatoms such as "heteroaryl". Examples of heteroaryl groups include C5-1QQ heteroaryl, C5_2 anthracene aryl, C5·丨5 heteroaryl, Cs-丨2 heteroaryl , Cs.ioheteroaryl, C5.7 heteroaryl, c5_6 heteroaryl, (:5heteroaryl and c6heteroaryl. Examples of monocyclic heterocycles include, but are not limited to, their derivatives Born from the following. N]: pyrrole (azole) (c5), pyridine (azine) (C6); 〇1: ° flu (oxocyclopentadiene) (c5); S!: thiophene (sulfur) (c5); Νθ〗: oxazole (C5), isoxazole (C5), isoxazine (c6); Ν2〇ι: ° dioxin (bite) (c5); Ν3〇ι: triazole (c5);
NiS】:噻唑(c5)、異噻唑(C5); N2 :咪唑(1,3-二唑)(c5)、吡唑(1,2-二唑)(c5)、。答嗓 (1,2-二嗪)(c6)、嘧啶(ι,3_二嗪)(C6)(例如,胞嘧。定 '胸腺 嘧啶、尿嘧啶)、吡嗪(1,4·二嗪)(C6); N3 :三唑(c5)、三嗪(c6);及, N4 :四唑(C5)。 包含稠環之雜環基團(其中一些亦為雜芳基)之實例包括 (但不限於): 衍生自下列之C9雜環基團·(具有2個稠環):笨并咬喃 (Οι)、異苯并吱喃(〇〇、吲哚(N〇、異吲哚(“I)、 冲(N,)、二氫吲哚(Νι)、異二氫吲哚(Νι)、嘌呤…4)(例 如,腺嘌呤、鳥嘌呤)、笨并咪唑(N2)、吲唑(N2)、笨并噁 1496l5.doc •55- 201111345 唑(ΝβΟ、笨并異°惡°坐(N〗〇1)、笨并二氧雜環戊二稀 (〇2)、苯并咬。占(N2〇丨)、苯并三°坐(N3)、苯并硫代°夫喃 (Sl)、苯并噻唑(NiS,)、苯并噻二唑(N2S); 衍生自下列之C1()雜環基團(具有2個稠環):咣烯(0〗)、 異啖烯(Οι)、苯并二氫哌喃(〇〇、異苯并二氫哌喃(〇1)、 苯并二噁炫基(〇2)、喹琳(Νι)、異喹琳(N〗)、喹p巾(Νι)、苯 并噁嗪(Ν〗〇ι)、苯并二嗪(NO、吼啶并。比啶(n2)、喹喏啉 (N2)、喹唑啉(N2) ' 啉(N2)、呔嗪(N2)、萘啶(n2)、喋啶 (N4); 衍生自苯并二氮呼(NO之Cn雜環基團(具有2個稠環); 衍生自下列之Cu雜環基團(具有3個稠環):。卡唑(Νι)、 二苯并°夫喃(〇ι)、二苯并°塞吩(S】)、。弄琳(n2)、坏咬(n2)、 吡啶并吲哚(N2);及, 衍生自下列之CM雜環基團(具有3個稠環):。丫咬(Νι) 咕噸(〇1)、硫代咕嘲(S〇、二苯并對二嚼英(a)、氧硫雜葱 (〇&)、吩嗪(n2)、吩噁嗪(Νι〇ι)、吩噻嗪(NiSi)、噻蒽 (s2)、啡啶(N〗)、啡啉(n2)、吩嗪(N2)。 “ 具有呈-NH-基團形式之氡援馬+ 八&虱%原子之雜環基團(包括雜乏 基)可經N-取代,即,呈鲁形式。舉例而言"比洛可奋 Ν·甲基取代,得到Ν·甲基。叫。N-取代基包括之實_ 不限於心成基、C3.2Q雜環基、C52G芳基及酿基。 Α)Γ取呈代:?團形式之氮環原子之雜環基團(包括㈣ 基)丄取代可呈N_氧化物形 ^ ―式。舉一 I496I5.doc 201111345 氧化物;°比°定可經取代’得到°比饥氧化物;笨并。夫咕可 經取代’得到苯并咬·氧化物(亦稱為苯并氧化咬喃)。 無論以上基團係單獨或為另一取代基之一部分,i自身 均可視情況可經-個或多個選自其自身及下文所列_ 取代基之基團取代。 風.-H。注意:若在特定位置之取代基係氫,則可方便 地將該化合物或基團看作在彼位置「未經取代」。 鹵基:-F、-Cl、-Br及-I。 羥基:-OH。 醚:-OR’其中R係醚取代基,例如,c"烷基(如下文 戶:論述,亦稱為(^.7院氧基)、c3_2。雜環基(亦稱為^雜 %基氧基)、或芳基(亦稱為q心芳基氧基),較佳係 Ci-7烧基。 ,、 烷氧基:-OR,其中R係烧基,例如,C丨-7炫基。CM 氧基之實例包括(但不限於甲氧基)、_〇Et(乙氧 基)/-〇_)(正丙氧基)、·〇(ίΡΓ)(異丙氧基卜〇(nBu)(正 丁氧基)、-o(sBu)(第二 丁氧基)、·0(ίΒυ)(異丁 氧基) 及-O(tBu)(第三丁氧基)。 縮醛:-CH(ORi)(OR2),其中尺丨及…獨立地為縮醛取代 基,例如,Cm烷基、(:^雜環基或Cs2〇芳基,較佳為ci7 烷基,或在「環狀」縮醛基團之情形下,及r2與其所連 接之兩個氧原子及其所連接之碳原子一起形成具有4個至8 個環原子之雜環。縮醛基團之實例包括(但不限於) 、-CH(〇Et)2及-CH(〇Me)(OEt)。 1496I5.doc •57· 201111345 側氧基(嗣基,-嗣):=〇。 硫酮(Thione,thioketone) : =8。 亞胺基(亞胺):=NR,其中R係亞胺基取代基例如, 氫、Cm烷基、C3^雜環基或Gw芳基,較佳係氫或cw烷 基。酯基團之實例包括(但不限於)=NH、=NMe、及 =NPh ° 曱醯基(曱醛(carbaldehyde,carboxaldehyde)) : _c(=c〇H。 醯基(酮基):-C(=0)R,其中r係醯基取代基,例如,a 7 烷基(亦稱為(^_7烷基醯基或Cl_7烷醯基)、C3_2g雜環基(亦 稱為C3.2〇雜環基醯基)或C5.2Q芳基(亦稱為c5 2()芳基醯基), 較佳係Ci·7炫《基。酿基之貫例包括(但不限於)_c(=〇)ch3 (乙醯基)、-C(=0)CH2CH3(丙醯基)、-c(=〇)C(CH3)3 (第三 丁醯基)及-C(=0)Ph(苯曱醯基、苯酮)。 羧基(羧酸):-C(=0)0H。 硫代羧基(硫代羧酸):-C(=S)SH。 硫羥羧基(硫羥羧酸):-C(=〇)SH。 硫羰羧基(硫羰羧酸):-C(=S)0H。 醋(叛酸酯(carboxylate,carboxylic acid ester)、氧裁 基):-C(=0)0R ’其中R係酯取代基,例如,Cl_7烷基、C3_20 雜環基或C5_2Q芳基’較佳係Ci_7烷基。酯基團之實例包括 (但不限於)-c(=o)och3、_c(=o)och2ch3、-c(=o)oc(ch3)3 及-C(=〇)〇Ph。 醯氧基(與酯相反):-〇C(=0)R,其中R係醯氧基取代 基’例如,Cw烷基、C3.2〇雜環基或c5_2()芳基,較佳為Cw 149615.doc -58· 201111345 烧基。醯氧基之實例包括(但不限於)_〇c(=〇)Cii3(乙醯氧 基)、-0C(=0)CH2CH3、-〇c( = 〇)c(CH3)3、-0C( = 0)Ph及 〇C(=0)CH2Ph。 氧基数基氧基:-〇C( = 〇)〇R,其中R係酯取代基,例 如’ C,·7烧基、(:3_2〇雜環基或c5 2()芳基,較佳係€17烷 基。S旨基團之實例包括(但不限於)_〇C( = 〇)〇CH3、 -OC(=0)〇CH2CH3 ' -〇C(=〇)〇C(CH3)3及-0C(=0)0Ph。 胺基:-nWr2 ’其中R1及R2獨立地為胺基取代基,例 如’氫、Cw烧基(亦稱為cN7烷基胺基或二_Cl7烷基胺 基)、C3-2〇雜環基或C5·^芳基,較佳為烷基,或在 「環狀」胺基之情形下’ R1及R2與其所連接之氮原子一起 形成具有4個至8個環原子之雜環。胺基可為一級(_nh2)、二 級(-NHR1)或三級(-NhWr2),在呈陽離子形式時,可為四級 。胺基之實例包括(但不限於)_而2、_NHCH3、 -NHC(CH3)2、-N(CH3)2、-N(CH2CH3)2及-NHPh。環狀胺基 之實例包括(但不限於)氮丙啶基、氮雜環丁基、吡咯啶 基、六氫咄啶基、六氫吡嗪基、嗎啉基及硫代嗎啉基。 醯胺基(胺基曱醯基(carbamoyl, carbamyl)、胺基羰基、 曱醯胺)·· -C(=0)NR〗R2,其中Ri及R2獨立地為胺基取代 基’如針對胺基所定義。醯胺基之實例包括(但不限於) -C(=0)NH2 > -C(=0)NHCH3 ' -C(=0)N(CH3)2 ' -C(=0)NHCH2CH3 及-C(=0)N(CH2CH3)2、以及其中Ri及r2與其所連接之氮原 子一起形成雜環結構之醯胺基,如在(例如)六氫吡啶基羰 基、嗎啉基羰基、硫代嗎啉基羰基及六氫吡嗪基羰基中。 1496i5.doc -59- 201111345 硫代醢胺基(硫代胺基甲醯基):_c(=s)NRlR2,其中汉,及 R2獨立地為胺基取代基,如針對胺基所定義。醯胺基之實 例包括(但不限於)-C(=S)NH2' -C(=S)NHCH3、<(=δ)Ν^Η3)2 及-C(=S)NHCH2CH3。 醞基醯胺基(醯基胺基):-Νί^(:(=〇)Κ_2,其中R〗係醯胺 取代基,例如,氫、Cw烷基、c:3^雜環基或匕心芳基, 較佳係Η或C! .7烧基’且R2係醯基取代基,例如,匸1 7烧 基、(^心雜環基或C5·^芳基,較佳係H或(:l·7烷基。醯胺基 團之實例包括(但不限於)-Nhc(=o)Ch3、-nhc(=o)ch2ch3 及-NHC(=〇)Ph。Ri及R2可一起形成環狀結構,如在(例如) 琥珀酿亞胺基、馬來醯亞胺基及鄰苯二曱醯亞胺基中:NiS]: thiazole (c5), isothiazole (C5); N2: imidazole (1,3-diazole) (c5), pyrazole (1,2-diazole) (c5),. Answer 嗓 (1,2-diazine) (c6), pyrimidine (ι, 3-diazine) (C6) (eg, cytosidine, thymidine, uracil), pyrazine (1,4-diazine) (C6); N3: triazole (c5), triazine (c6); and, N4: tetrazole (C5). Examples of heterocyclic groups containing fused rings (some of which are also heteroaryl) include, but are not limited to: C9 heterocyclic groups derived from the following (with 2 fused rings): stupid and biting (Οι ), isobenzopyrene (〇〇, 吲哚 (N〇, isoindole ("I), rush (N,), dihydroanthracene (Νι), isoindoline (Νι), 嘌呤... 4) (eg, adenine, guanine), stupid imidazole (N2), carbazole (N2), stupid and evil 1496l5.doc • 55- 201111345 azole (ΝβΟ, stupid and different ° ° ° sit (N〗 〇 1), stupid and dioxolane (〇2), benzo bite. (N2〇丨), benzotriene (N3), benzothiazepine (Sl), benzo Thiazole (NiS,), benzothiadiazole (N2S); derived from the following C1 () heterocyclic group (having 2 fused rings): terpene (0), isodecene (Οι), benzo Dihydropyran (〇〇, isobenzopyran (〇1), benzodioxan (〇2), quinoline (Νι), isoquine (N)), quinine p towel (Νι ), benzoxazine (Ν〗 〇ι), benzodiazine (NO, acridine, pyridine (n2), quinoxaline (N2), quinazoline (N2)' Porphyrin (N2), pyridazine (N2), naphthyridine (n2), acridine (N4); derived from benzodiazepine (Cn heterocyclic group of NO (having 2 fused rings); derived from Cu heterocyclic group (having 3 fused rings): carbazole (Νι), dibenzofuran (〇ι), dibenzoxe (S), 琳琳(n2), bad Bite (n2), pyridine oxime (N2); and, derived from the following CM heterocyclic group (having 3 fused rings): bite (Νι) 咕 ton (〇1), thio 咕 ( ( S〇, dibenzo-p-butyl chelate (a), oxysulfide (〇 &), phenazine (n2), phenoxazine (Νι〇ι), phenothiazine (NiSi), thiazide (s2) ), phenidine (N), phenanthroline (n2), phenazine (N2). "Heterocyclic group with a -NH- group in the form of a supportive horse + eight & 虱% atom (including lack of The base may be N-substituted, that is, in the form of a ruthenium. For example, " piroxicam methyl substituted, Ν·methyl. Called. N-substituent includes _ not limited to heart-based , C3.2Q heterocyclic group, C52G aryl group and aryl group. Α) Extraction: a heterocyclic group of a nitrogen ring atom in the form of a group (including (4) groups) The substitution can be N_oxide form ^-type. Take an I496I5.doc 201111345 oxide; ° ratio can be replaced by 'to get ° than hunger oxide; stupid. Fuxi can be substituted 'to get benzo bite · Oxide (also known as benzoxylene). Whether the above groups are alone or part of another substituent, i itself may optionally be replaced by one or more selected from itself and _ listed below Substituting for the group. Wind.-H. Note: If the substituent at a particular position is hydrogen, the compound or group can conveniently be considered "unsubstituted" at that position. Halogen groups: -F, -Cl, -Br and -I. Hydroxyl: -OH. Ether: -OR' wherein R is an ether substituent, for example, c"alkyl (hereinafter, as discussed, also known as (^.7 oxy), c3_2. Heterocyclyl (also known as heteropoly) Oxy), or aryl (also known as q-aryl aryloxy), preferably Ci-7 alkyl., alkoxy: -OR, wherein R is an alkyl group, for example, C丨-7 Examples of CM oxy groups include, but are not limited to, methoxy, 〇Et(ethoxy)/-〇_)(n-propoxy), 〇(ίΡΓ)(isopropoxy oxime ( nBu)(n-butoxy), -o(sBu)(second butoxy), ·0(ίΒυ)(isobutoxy) and -O(tBu)(third butoxy). Acetal: -CH(ORi)(OR2), wherein the oxime and ... are independently acetal substituents, for example, Cm alkyl, (:^heterocyclyl or Cs2 aryl, preferably ci7 alkyl, or In the case of a cyclic "acetal group", and r2 together with the two oxygen atoms to which it is attached and the carbon atom to which it is attached form a heterocyclic ring having 4 to 8 ring atoms. Examples of acetal groups include But not limited to), -CH(〇Et)2 and -CH(〇Me)(OEt). 1496I5.doc •57· 201111345 Side oxy (anthracene, -嗣):=〇 Thione, thioketone: = 8. Imino group (imine): =NR, wherein the R-based imido substituent is, for example, hydrogen, Cm alkyl, C3^heterocyclyl or Gw aryl, preferably Hydrogen or cw alkyl. Examples of ester groups include, but are not limited to, =NH, =NMe, and =NPh ° carbaldehyde (carboxaldehyde): _c (=c〇H. fluorenyl) (keto group): -C(=0)R, wherein r is a mercapto substituent, for example, a 7 alkyl (also known as (^_7 alkylsulfonyl or Cl-7 alkenyl), C3_2g heterocyclyl ( Also known as C3.2 〇heterocyclyl fluorenyl) or C5.2Q aryl (also known as c5 2 () aryl fluorenyl), preferably Ci·7 炫 "basis. But not limited to) _c (= 〇) ch3 (acetyl group), -C (=0) CH2CH3 (propyl group), -c (= 〇) C (CH3) 3 (third butyl group) and -C (= 0) Ph (phenyl fluorenyl, benzophenone). Carboxy (carboxylic acid): -C(=0)0H. Thiocarboxy (thiocarboxylic acid): -C(=S)SH. Thiocarboxyl (sulfur) Hydroxycarboxylic acid): -C(=〇)SH. Thiocarbonylcarboxyl (thiocarbonylcarboxylic acid): -C(=S)0H. Vinegar (carboxylate, carboxylic acid ester, oxygen cutting):- C(=0)0R 'its R based ester substituent, e.g., Cl_7 alkyl, C3_20 aryl, heterocyclyl or C5_2Q 'preferred system Ci_7 alkyl group. Examples of ester groups include, but are not limited to, -c(=o)och3, _c(=o)och2ch3, -c(=o)oc(ch3)3, and -C(=〇)〇Ph. Alkoxy (in contrast to ester): -〇C(=0)R, wherein R is a methoxy substituent 'for example, Cw alkyl, C3.2 fluorenyl or c5_2() aryl, preferably Cw 149615.doc -58· 201111345 Burning base. Examples of decyloxy groups include, but are not limited to, _〇c(=〇)Cii3(acetoxy), -0C(=0)CH2CH3, -〇c(= 〇)c(CH3)3, -0C ( = 0) Ph and 〇C(=0)CH2Ph. Oxyloxy group: -〇C(=〇)〇R, wherein R is an ester substituent such as 'C,·7 alkyl, (3/2〇 heterocyclic or c5 2) aryl, preferably Examples of the group of S17 alkyl groups include (but are not limited to) _〇C(= 〇)〇CH3, -OC(=0)〇CH2CH3 ' -〇C(=〇)〇C(CH3)3 and -0C(=0)0Ph. Amino group: -nWr2 ' wherein R1 and R2 are independently an amino substituent such as 'hydrogen, Cw alkyl (also known as cN7 alkylamino or di-Cl7 alkylamino) And a C3-2〇heterocyclyl group or a C5·^aryl group, preferably an alkyl group, or in the case of a "cyclic" amine group, R1 and R2 together with the nitrogen atom to which they are attached form 4 to 8 a heterocyclic ring of a ring atom. The amine group may be a primary (_nh2), a secondary (-NHR1) or a tertiary (-NhWr2), and in the form of a cation, may be a quaternary. Examples of the amine include, but are not limited to And _NHCH3, -NHC(CH3)2, -N(CH3)2, -N(CH2CH3)2, and -NHPh. Examples of cyclic amine groups include, but are not limited to, aziridine, aza Cyclobutyl, pyrrolidinyl, hexahydroacridinyl, hexahydropyrazinyl, morpholinyl and thiomorpholinyl. Amidino (amino thiol) Carbamoyl, carbamyl), aminocarbonyl, decylamine···C(=0)NR R2, wherein Ri and R2 are independently an amino substituent, as defined for an amine group. Examples of guanamine groups include (but not limited to) -C(=0)NH2 > -C(=0)NHCH3 ' -C(=0)N(CH3)2 ' -C(=0)NHCH2CH3 and -C(=0)N(( CH2CH3)2, and amidino group in which Ri and r2 together with the nitrogen atom to which they are attached form a heterocyclic structure, such as, for example, hexahydropyridylcarbonyl, morpholinylcarbonyl, thiomorpholinylcarbonyl, and hexahydro In the pyrazinylcarbonyl group. 1496i5.doc -59- 201111345 Thioguanamine (thioaminocarbamyl): _c(=s)NRlR2, wherein han, and R2 are independently an amine substituent, such as The definition of the amine group includes, but is not limited to, -C(=S)NH2'-C(=S)NHCH3, <(=δ)Ν^Η3)2 and -C(=S) NHCH2CH3. Indolyl (mercaptoamine): -Νί^(:(=〇)Κ_2, wherein R is a guanamine substituent, for example, hydrogen, Cw alkyl, c: 3^heterocyclyl or oxime An aryl group, preferably a hydrazine or a C?.7 alkyl group and an R2 fluorenyl substituent, for example, a hydrazine group, a heterocyclic group or a C5 aryl group, preferably H or Examples of the alkylamine group include, but are not limited to, -Nhc(=o)Ch3, -nhc(=o)ch2ch3, and -NHC(=〇)Ph. Ri and R2 may form a ring together. a structure such as, for example, amber-based imine, maleimine, and phthalimide:
琥珀醯亞胺基 馬來醯亞胺基 鄰苯二曱醯亞胺基 胺基羰基氧基:-0C(=0)NR丨R2,其中以及尺2獨立地為 胺基取代基,如針對胺基所定義。胺基羰基氧基之實例包 括(但不限於)-0C(=0)NH2、-OC(=0)NHMe、-〇C(=〇)NMe2 及-OC(=0)NEt2。 脲基:-N(R〗)CONR2R3,其中R2及R3獨立地為胺基取代 基’如針對胺基所定義,且R1係脲基取代基,例如,氫、 C丨―7烷基、(:3_2〇雜環基或(:5-2〇芳基,較佳係氫或C丨·7烧基。 脲基之實例包括(但不限於)-NHCONH2、-NHCONHMe、 -NHCONHEt、_NHCONMe2、_NHCONEt2、-NMeCONH2Amber quinone imine, maleimide, phthalimido, imino, carbonyloxy: - 0C (=0) NR 丨 R2, wherein the sizing 2 is independently an amine substituent, such as for an amine Base definition. Examples of the aminocarbonyloxy group include, but are not limited to, -0C(=0)NH2, -OC(=0)NHMe, -〇C(=〇)NMe2, and -OC(=0)NEt2. Urea group: -N(R)CONR2R3, wherein R2 and R3 are independently an amine substituent 'as defined for an amine group, and R1 is a ureido substituent, for example, hydrogen, C丨-7 alkyl, ( : 3 2 〇heterocyclyl or (: 5-2 aryl, preferably hydrogen or C 丨 7 alkyl. Examples of ureido include, but are not limited to, -NHCONH2, -NHCONHMe, -NHCONHEt, _NHCONMe2, _NHCONEt2 ,-NMeCONH2
149615.doc 201111345149615.doc 201111345
、-NMeCONHMe、-NMeCONHEt、-NMeCONMeJ -NMeCONEt2。 四唑基:具有四個氮原子及一個碳原子之五員芳香族 環,, -NMeCONHMe, -NMeCONHEt, -NMeCONMeJ -NMeCONEt2. Tetrazolyl: a five-membered aromatic ring with four nitrogen atoms and one carbon atom.
亞胺基:=NR ’其中R係亞胺基取代基,例如,氫、^ ; 烧基、C3.2。雜環基或C5.2g芳基’較佳係Η或Cm院基。亞胺 基之實例包括(但不限於)=NH、=NMe及=NEt。 脒(脉基):-C(=NR)NR2 ’其中每一 R皆為脒取代基,例 如,氫、Cu烷基、C3_2〇雜環基或Cmo芳基,較佳為11或 Cu炫基。脒基團之實例包括(但不限於)_c(=nh>NH2、 -C(=NH)NMe2&-C(=NMe)NMe2。 硝基:-N02。 亞硝基:-NO。 氰基(腈(nitrile,carbonitrile)) : -CN。 異氰基:-NC。 氰氧基:-OCN。 異氰氧基:-NCO。 硫代氱基(硫代氰氧基):-SCN。 異硫代氰基(異硫代氰氧基):_N(:S。 在大多數情形下’取代基自身係經取代的。 舉例而言,Cm烷基可經(例如)以下基團取代: 羥基(亦稱為羥基-Cw烷基); 149615.doc -61 · 201111345 鹵基(亦稱為鹵基-Cw烷基); 胺基(亦稱為胺基-Cm烷基); 羧基(亦稱為羧基-Cw烷基);Imino group: =NR ' wherein R is an imido substituent, for example, hydrogen, ^; alkyl, C3.2. A heterocyclic group or a C5.2 g aryl group is preferably a hydrazine or a Cm-based group. Examples of imido groups include, but are not limited to, =NH, =NMe, and =NEt.脒(R): -C(=NR)NR2 ' wherein each R is a hydrazine substituent, for example, hydrogen, Cu alkyl, C3_2 fluorenyl or Cmo aryl, preferably 11 or Cu thio . Examples of oxime groups include, but are not limited to, _c(=nh>NH2, -C(=NH)NMe2&-C(=NMe)NMe2. Nitro:-N02. Nitroso:-NO. Cyano ( Nitrile (carbonitrile): -CN. Isocyano: -NC. Cyanooxy group: -OCN. Isocyanato group: -NCO. Thioguanidino (thiocyanooxy): -SCN. Cyano (isothiocyanooxy): _N(:S. In most cases the 'substituent itself is substituted. For example, a Cm alkyl group may be substituted by, for example, the following group: hydroxy ( Also known as hydroxy-Cw alkyl); 149615.doc -61 · 201111345 Halo (also known as halo-Cw alkyl); amine (also known as amino-Cm alkyl); carboxyl (also known as Carboxyl-Cw alkyl);
Cl·7烧氧基(亦稱為Cl.7烧氧基- Cl.7院基)· C5-2 0芳基(亦稱為 C5-2O 芳基-C!··;烷基)。 同樣’ C5_2〇芳基可經(例如)以下基團取代: 輕基(亦稱為經基-C5-2Q芳基); 齒基(亦稱為鹵基-C 5 - 2 0芳基); 胺基(亦稱為胺基-C5_2〇芳基,例如,如在笨胺中). 羧基(亦稱為羧基-C5_2〇芳基,例如,如在笨甲酸中). C〗-7燒基(亦稱為Cw烧基芳基,例如,如在甲笨 中); ^ C〗-7烧氧基(亦稱為C〗·7烷氧基-Cs-M芳基,例如,如在苯 甲醚中); C5-2〇芳基(亦稱為C5.2〇芳基-C5-2〇芳基,例如,如在聯笨 中)。 該等經取代之取代基之此等及其他具體實例將在下文中 予以闡述。 羥基-C〗·7烷基:本文所用術語「羥基_c〗7烷基」係指其 中至少一個氩原子(例如’ 1個、2個、3個)已由羥基代替 之Cl·?烷基。該等基團之實例包括(但不限於)_ch2〇h、 -CH2CH2OH及-ch(oh)ch2oh。 i基-Ci·7烷基:本文所用術語「鹵基_Cl-7烷基」係指其 中至少一個氫原子(例如,1個、2個、3個)已由鹵素原子 149615.doc •62- 201111345 (例如,:F、Cl、Br·、I)代替之Cm烷基。若不止一個氫原子 已由鹵素原子代替’則該等画素原子可獨立地相同或不 同。母個風原子皆可由鹵素原子代替,在該情形下,該基 團可方便地稱為「Cw全鹵代烷基」。該等基團之實例包括 (但不限於)-cf3、-chf2、-CH2F、-CC13、_CBr3、_CH2CH2f 、-CH2CHF2&-CH2CF3。 胺基-c〗·7烷基:本文所用術語「胺基_Ci7烷基」係指其 中至少一個氫原子(例如,1個、2個、3個)已由胺基代替 之(^-7烧基。該.等基團之實例包括(但不限於)_CH2NH2、 -CH2CH2NH2及-CH2CH2N(CH3)2。 羧基-C,-7烷基:本文所用術語「羧基_Ci 7烷基」係指其 中至少一個氫原子(例如,1個、2個、3個)已由羧基代替 之烷基。該等基團之實例包括(但不限於)_Ch2c〇〇h及 -CH2CH2COOH。 C!-7烷氧基-C〗·7烷基:本文所用術語「Cw烷氧基-Cw烷 基」係指其中至少一個氫原子(例如,1個、2個、3個)已由 C〗·7烷氧基代替之Cw烷基。該等基團之實例包括(但不限 於)-CH2OCH3、-CH2CH2OCH3及-CH2CH2OCH2CH3。 C5-2〇芳基-Cu烷基:本文所用術語「c5.20芳基-Cw烷 基」係指其中至少一個氫原子(例如,1個、2個、3個)已由 C5-2〇芳基代替之Ci.7烷基。該等基團之實例包括(但不限 於)苄基(苯基曱基、PhCH2-)、二苯甲基(Ph2CH-)、三苯甲 基(三苯基曱基、Ph3C-)、苯乙基(苯基乙基、Ph-CH2CH2-) 、苯乙烯基(Ph-CH=CH-)、肉桂基(Ph-CH=CH-CH2-)。 149615.doc -63- 201111345 羥基-c5_20芳基:本文所用術語「經基-c5_20芳基」係指 其中至少一個氫原子(例如’ 1個、2個、3個)已由羥基取代 之C5_2()芳基。該等基團之實例包括(但不限於)彼等衍生自 下列者:苯酴、蔡驗、鄰苯二紛、間苯二酌·、對苯二酴、 連苯三酚、間苯三酚。 鹵基-C5-20芳基:本文所用術語「鹵基-c5.20芳基」係指 其中至少一個氫原子(例如’ 1個、2個、3個)已經鹵基(例 如,F、CM、Br、I)取代之C5.2()芳基。該等基團之實例包括 (但不限於)鹵代笨基(例如,鄰-、間-或對-取代之氟苯基、 氯苯基、溴苯基或碘苯基)、二_代苯基、三齒代苯基、 四鹵代苯基及五函代苯基。 C!·7烷基-C5.20芳基:本文所用術語「c!_7烷基-C5_20芳 基」係指其中至少一個氫原子(例如,1個、2個、3個)已經 Cl·?烧基取代之c5.2Q芳基。該等基團之實例包括(但不限 於)曱苯基(來自甲苯)、二甲苯基(來自二曱苯)、均三曱苯 基(來自均二曱苯)及異丙苯基(cumenyl,curnyl)(來自異丙 苯)、及均四甲苯基(來自均四甲苯)。Cl.7 alkoxy (also known as Cl.7 alkoxy-Cl.7). C5-2 0 aryl (also known as C5-2O aryl-C!.; alkyl). Similarly, the 'C5_2 aryl group can be substituted with, for example, the following groups: a light group (also known as a trans-C5-2Q aryl group); a dentate group (also known as a halo-C 5 - 20 aryl group); Amino group (also known as amino-C5 2 fluorene aryl group, for example, as in a strepamine). Carboxyl group (also known as carboxy-C5 2 fluorene aryl group, for example, as in benzoic acid). C -7 -7 alkyl group (also known as Cw alkyl aryl, for example, as in phenyl); ^ C -7 alkoxy (also known as C -7 alkoxy-Cs-M aryl, for example, as in benzene Methyl ether); C5-2 anthracene aryl (also known as C5.2 aryl)-C5-2 aryl, for example, as in phenyl. These and other specific examples of such substituted substituents are set forth below. Hydroxy-C-7 alkyl: The term "hydroxy-c" 7 alkyl as used herein refers to a Cyl group in which at least one argon atom (eg, '1, 2, 3) has been replaced by a hydroxy group. . Examples of such groups include, but are not limited to, _ch2〇h, -CH2CH2OH, and -ch(oh)ch2oh. i-Ci·7 alkyl: The term "halo-Cl-7 alkyl" as used herein means that at least one hydrogen atom (for example, 1, 2, 3) has been halogen atom 149615.doc • 62 - 201111345 (for example: F, Cl, Br·, I) instead of Cm alkyl. If more than one hydrogen atom has been replaced by a halogen atom, then the pixel atoms may be independently the same or different. The parent wind atom may be replaced by a halogen atom, and in this case, the group may be conveniently referred to as "Cw perhaloalkyl group". Examples of such groups include, but are not limited to, -cf3, -chf2, -CH2F, -CC13, _CBr3, _CH2CH2f, -CH2CHF2&-CH2CF3. Amino-c -7 alkyl: The term "amino-Ci7 alkyl" as used herein means that at least one of the hydrogen atoms (for example, 1, 2, 3) has been replaced by an amine group (^-7). Examples of such groups include, but are not limited to, _CH2NH2, -CH2CH2NH2, and -CH2CH2N(CH3)2. Carboxyl-C, -7 alkyl: The term "carboxy-Ci7 alkyl" as used herein refers to An alkyl group in which at least one hydrogen atom (for example, 1, 2, 3) has been replaced by a carboxyl group. Examples of such groups include, but are not limited to, _Ch2c〇〇h and -CH2CH2COOH. Oxy-C 7 alkyl: The term "Cw alkoxy-Cw alkyl" as used herein means that at least one of the hydrogen atoms (eg, 1, 2, 3) has been a C alkoxy Substituting Cw alkyl. Examples of such groups include, but are not limited to, -CH2OCH3, -CH2CH2OCH3, and -CH2CH2OCH2CH3. C5-2 aryl-Cualkyl: The term "c5.20 aryl-Cw" as used herein. "Alkyl" means a Ci.7 alkyl group in which at least one hydrogen atom (for example, 1, 2, 3) has been replaced by a C5-2 aryl group. Examples of such groups include, but are not limited to, Benzyl (phenyl Sulfhydryl, PhCH2-), diphenylmethyl (Ph2CH-), trityl (triphenylsulfonyl, Ph3C-), phenethyl (phenylethyl, Ph-CH2CH2-), styryl ( Ph-CH=CH-), cinnamyl (Ph-CH=CH-CH2-). 149615.doc -63- 201111345 Hydroxy-c5_20 aryl: The term "radio-c5_20 aryl" as used herein means at least one of A hydrogen atom (e.g., '1, 2, 3) C5_2() aryl groups which have been replaced by a hydroxy group. Examples of such groups include, but are not limited to, those derived from the group consisting of benzoquinone, cil, O-benzoic acid, isophthalonitrile, p-benzoquinone, pyrogallol, phloroglucinol. Halo-C5-20 aryl: The term "halo-c5.20 aryl" as used herein refers to At least one hydrogen atom (eg, '1, 2, 3') has a C5.2() aryl group substituted with a halo group (eg, F, CM, Br, I). Examples of such groups include (but It is not limited to a halogenated styl group (for example, o-, m- or p-substituted fluorophenyl, chlorophenyl, bromophenyl or iodophenyl), di-phenyl, tridentate phenyl, tetra Halophenyl and pentaphenyl. C!·7 alkyl-C5.20 aryl: The term "c!_7 alkyl-C5_20 aryl" means a c5.2Q aryl group in which at least one hydrogen atom (for example, 1, 2, 3) has been substituted with a Cl. group. Examples include, but are not limited to, decyl phenyl (from toluene), xylyl (from diphenyl), mesitylene (from benzoquinone), and cumenyl (curnyl) (from Cumene), and a tetramethylphenyl group (from tetramethylbenzene).
經基-C,-7烷氧基:_〇R,其中R係羥基_Ci 7烷基。羥基_ C,-7院氧基之實例包括(但不限於)_〇ch2〇h、-〇CH2CH2OH 及-och2ch2ch2oh。 齒基-C!·7烷氧基:-〇R,其中R係鹵基_Cl 7烷基。鹵 基-Cl·7烧氧基之實例包括(但不限於)-OCF3、-OCHF2、 _OCH2F、_〇cci3、-〇CBr3、-OCH2CH2F、_OCH2CHF2及 -OCH2CF3 0 149615.doc -64- 201111345Peryl-C,-7 alkoxy: _ 〇 R, wherein R is hydroxy-Ci 7 alkyl. Examples of hydroxy-C,-7-houseoxy include, but are not limited to, _〇ch2〇h, -〇CH2CH2OH, and -och2ch2ch2oh. Tenetyl-C!·7 alkoxy: -〇R, wherein R is halo-Cl 7 alkyl. Examples of halo-Cl.7 alkoxy groups include, but are not limited to, -OCF3, -OCHF2, _OCH2F, _〇cci3, -〇CBr3, -OCH2CH2F, _OCH2CHF2, and -OCH2CF3 0 149615.doc -64- 201111345
羧基-C!·7烷氧基:-OR ’其中R係羧基_Cl 7烷基。羧基_Ci 7 烧氧基之實例包括(但不限於)-0CH2C00H、-0CH2CH2C00H 及-och2ch2ch2cooh。Carboxy-C!·7 alkoxy group: -OR ' wherein R is a carboxyl group - a C 7 alkyl group. Examples of the carboxy-Ci 7 alkoxy group include, but are not limited to, -0CH2C00H, -0CH2CH2C00H, and -och2ch2ch2cooh.
Ci-7烧氧基-Cw烧氧基·· -OR’其中R係CN7烧氧基-Ci-7烧 基。C〗·7烷氧基-CN7烷氧基之實例包括(但不限於)_0CH20CH3 、-och2ch2och3及-och2ch2och2ch3。 C5-20芳基-CN7烷氧基:-〇R,其中R係c5_20芳基-Ci-7烷 基。該等基團之實例包括(但不限於)苄基氧基、二苯曱基 氧基、三苯曱基氧基、苯乙氧基、苯乙烯基氧基及肉桂基 氧基。Ci-7 alkoxy-Cw alkoxy-·OR' wherein R is a CN7 alkoxy-Ci-7 alkyl group. Examples of C alkoxy-CN7 alkoxy include, but are not limited to, 0CH20CH3, -och2ch2och3, and -och2ch2och2ch3. C5-20 aryl-CN7 alkoxy: -〇R, wherein R is a c5_20 aryl-Ci-7 alkyl group. Examples of such groups include, but are not limited to, benzyloxy, diphenylphosphonyloxy, triphenylphosphoniumoxy, phenethyloxy, styryloxy, and cinnamyloxy.
Cu烷基-c5_20芳基氧基:-OR,其中R係Cw烷基-C5_20 芳基。該等基團之實例包括(但不限於)甲苯基氧基、二曱 苯基氧基、三甲苯基氧基、異丙苯基氧基及均四甲苯基氧 基。 胺基-CU7烷基-胺基:本文所用術語「胺基-CK7烷基-胺 基」係指其中取代基R1或R2中之一者自身係胺基_Cl7烷基 (-C!·?烷基-NR3R4)之胺基-NRiR2。胺基-Ci-7烷基胺基可由 (例如)式-NRi-Cw烷基-NR3R4代表。該等基團之實例包括 (但不限於)式-NR^CH^nWR2之基團,其中η係1至6(例 如-NHCH2NH2、_NH(CH2)2NH2、-NH(CH2)3NH2、 -NH(CH2)4NH2 ' -NH(CH2)5NH2 ' -NH(CH2)6NH2) ' -NHCH2NH(Me)、-NH(CH2)2NH(Me)、-NH(CH2)3NH(Me) ' -NH(CH2)4NH(Me) ' -NH(CH2)5NH(Me) > -NH(CH2)6NH(Me) 、-NHCH2NH(Et)、-NH(CH2)2NH(Et)、-NH(CH2)3NH(Et) 149615.doc •65- 201111345 、-NH(CH2)4NH(Et)、-NH(CH2)5NH(Et)及-NH(CH2)6NH(Et)。 一些較佳之取代基 在一個較佳實施例中,各取代基(在本文中通常稱為R) 獨立地選自:鹵基;羥基;醚(例如,C]-7烷氧基);甲醯 基;醯基(例如,C,-7烷基醯基、C5-2G芳基醯基);醯基 鹵;羧基;酯;醯氧基;醯胺基;醯基醯胺基;硫代醯胺 基;四唑基;胺基;硝基;亞硝基;疊氮基;氰基;異氰 基;氰氧基;異氰氧基;硫代氰基;異硫代氰基;毓基; 硫醚(例如,Cw烷基硫基);磺酸;磺酸酯;砜;磺醯基 氧基;亞磺醯基氧基;磺胺基;磺醯胺基;亞磺醯胺基; 胺磺醯基;亞磺醯胺基;cN7烷基(包括(例如)未經取代之 Ci.7烧基、Ci.7齒基院基、Cw經基烧基、Ci-7缓基院基、 C〗-7胺基烷基、c5.20芳基-Cu烷基);C3_2(3雜環基;或c5_20 ^基(包括(例如)〇5·20碳芳基、C5.2〇雜芳基、(3丨-7烧基-(1:5_2〇 方基及C5-2O鹵基芳基))。Cu alkyl-c5_20 aryloxy: -OR, wherein R is a Cw alkyl-C5_20 aryl group. Examples of such groups include, but are not limited to, tolyloxy, decyloxy, tricyloxy, cumyloxy, and tetramethyltolyloxy. Amino-CU7 alkyl-amino group: As used herein, the term "amino-CK7 alkyl-amino" refers to one of the substituents R1 or R2 which is itself an amine group -Cl7 alkyl (-C!?? Amino-NR3R4) Amino-NRiR2. The amino-Ci-7 alkylamine group can be represented, for example, by the formula -NRi-Cwalkyl-NR3R4. Examples of such groups include, but are not limited to, groups of the formula -NR^CH^nWR2 wherein η is 1 to 6 (eg, -NHCH2NH2, _NH(CH2)2NH2, -NH(CH2)3NH2, -NH( CH2)4NH2 '-NH(CH2)5NH2 '-NH(CH2)6NH2) '-NHCH2NH(Me), -NH(CH2)2NH(Me), -NH(CH2)3NH(Me) '-NH(CH2) 4NH(Me) '-NH(CH2)5NH(Me) > -NH(CH2)6NH(Me), -NHCH2NH(Et), -NH(CH2)2NH(Et), -NH(CH2)3NH(Et 149615.doc •65- 201111345, -NH(CH2)4NH(Et), -NH(CH2)5NH(Et) and -NH(CH2)6NH(Et). Some preferred substituents In a preferred embodiment, each substituent (generally referred to herein as R) is independently selected from the group consisting of: halo; hydroxy; ether (e.g., C]-7 alkoxy); formazan Base; sulfhydryl (eg, C, -7 alkyl fluorenyl, C5-2G aryl fluorenyl); fluorenyl halide; carboxyl; ester; decyloxy; decylamino; fluorenyl amide; Amine; tetrazolyl; amine; nitro; nitroso; azide; cyano; isocyano; cyanooxy; isocyanato; thiocyano; isothiocyano; Sulfone (for example, Cw alkylthio); sulfonic acid; sulfonate; sulfone; sulfonyloxy; sulfinyloxy; sulfonyl; sulfonylamino; sulfinamide; a sulfonyl group; a sulfinylamino group; a cN7 alkyl group (including, for example, an unsubstituted Ci.7 alkyl group, a Ci.7 tooth base group, a Cw base group, a Ci-7 slow base group, C -7 aminoalkyl, c5.20 aryl-Cu alkyl); C3_2 (3 heterocyclic; or c5_20 ^ group (including, for example, 〇5·20 carbon aryl, C5.2 〇 aryl) Base, (3丨-7 alkyl-(1:5_2〇 group and C5-2O haloaryl)).
在一個較佳實施例中’各取代基(在本文中通常稱為R) 獨立地選自:-F、-Cl、-Br、-I、-OH、-OMe、-〇Et、-SH 、-SMe ' -SEt、-C(=0)Me、-C(=0)0H、-C(=0)OMe、-CONH2 、-CONHMe、-NH2、-NMe2、-NEt2、_N(nPr)2、-N(iPr)2 、-CN、-N02、-Me、-Et、-CF3、-OCF3、-CH2OH、-CH2CH2OH 、-CH2NH2、-CH2CH2NH2及-Ph。 在一個較佳實施例中,各取代基(在本文中通常稱為R) 獨立地選自:羥基;醚(例如,Cl.7烷氧基);酯;醯胺 基;胺基;及(:〗-7烷基(包括(例如)未經取代之cN7烧基、 149615.doc -66- 201111345In a preferred embodiment 'each substituent (commonly referred to herein as R) is independently selected from: -F, -Cl, -Br, -I, -OH, -OMe, -〇Et, -SH, -SMe ' -SEt, -C(=0)Me, -C(=0)0H, -C(=0)OMe, -CONH2, -CONHMe, -NH2, -NMe2, -NEt2, _N(nPr)2 -N(iPr)2, -CN, -N02, -Me, -Et, -CF3, -OCF3, -CH2OH, -CH2CH2OH, -CH2NH2, -CH2CH2NH2, and -Ph. In a preferred embodiment, each substituent (generally referred to herein as R) is independently selected from the group consisting of: a hydroxyl group; an ether (e.g., a Cl.7 alkoxy group); an ester; an amidino group; an amine group; : -7 alkyl group (including, for example, unsubstituted cN7 alkyl, 149615.doc -66- 201111345
Ci·7齒基烷基、Ci 7羥基烷基 基、C5_2〇芳基_Ci 7烷基)。Ci·7-dentylalkyl, Ci 7hydroxyalkyl, C5 2〇aryl_Ci 7 alkyl).
Ci-7竣基烧基、Cw胺基烧 現將參照附圖闡述本發明 參照以下實例(其為本發 明。 之實施例,其中: 明之實施例)進一步闡述本發 儘管許多特徵已在實例中在特徵之具體組合之内容中提 及’且若適當’在彼等特徵具有特定值之情形下,但應理 解彼等特徵中之任一者皆可與或不與其他特徵一起存在於 :發明之其他實施例中。同樣,任―與特徵有關之特定值 皆可根據本文所給出之一般揭示内容加以調節。 儀器及表徵方法 核磁共振(NMR)光譜係使用氯仿-(1或二氣甲烷_d2作為溶 劑並使用四甲基矽烷(TMS)作為内標在仏以“ Dpx 4〇〇 MHz光譜儀上收集。 基質辅助雷射解吸/電離飛行時間(MALDI-TOF)質譜係 在 Bruker Autoflex TOF/TOF儀器上獲得。 差示掃描量熱(DSC)係在氮下在TA儀器DSC 2920模組上 (掃描速率為2〇°C/min)實施。 熱重分析(TGA)係使用TA儀器TGA 2050模組(加熱速率 為20°C/min)來實施。 循環伏安(CV)實驗係在恒電位分析儀(PGSTAT30型)上 實施。所有CV量測均係在二氣甲烷中利用0.1 Μ四丁基六 氟磷酸銨作為支持電解質(掃描速率為50 mV/s)使用由鉑絲 工作電極 '金反電極及存於3 M KC1中之Ag/AgCl參考電極 149615.doc -67- 201111345 組成之習用三電極組態來記錄β Ύ 將所篁測電位轉化成 SCE(飽和甘录電極)並以·4·4 eV作為相對於真空之似能 級自起始氧化還原電位得到相應電離電位(Ip)及電子親和 力(EA)值(EA=E 還原起始+4.4 eV,IP=Ea 化起始+4 4 eV)。 吸收光譜係使用濃度介於1·8χ1〇-6至3 1χ1〇_6 M之間(除 非另有說明)的二氣甲烧溶液在Shimadzu UV-3101 PC UV-vis-NIR分光光度計上記錄。 合成 以下反應圖顯示用於製備本發明雙極化合物之方法。 149615.doc -68- 201111345Ci-7 mercaptoalkyl, Cw amine based calcination will be described with reference to the accompanying drawings in which the following examples (which are examples of the invention, wherein: the embodiments of the invention) further illustrate the present invention, although many features are in the examples In the context of a particular combination of features, reference is made to 'and where appropriate' where the features have particular values, but it should be understood that any of the features may or may not be present with other features: In other embodiments. Similarly, any particular value associated with a feature may be adjusted according to the general disclosure given herein. Apparatus and Characterization Methods Nuclear magnetic resonance (NMR) spectroscopy was performed using chloroform-(1 or di-methane methane_d2 as a solvent and using tetramethyl decane (TMS) as an internal standard on a Dpx 4 〇〇 MHz spectrometer. Auxiliary Laser Desorption/Ionization Time of Flight (MALDI-TOF) mass spectrometry was obtained on a Bruker Autoflex TOF/TOF instrument. Differential Scanning Calorimetry (DSC) was performed on a TA instrument DSC 2920 module under nitrogen (scan rate 2 〇°C/min). Thermogravimetric analysis (TGA) was performed using a TA instrument TGA 2050 module (heating rate of 20 °C/min). Cyclic voltammetry (CV) was performed on a potentiostat analyzer (PGSTAT30). All of the CV measurements were carried out in a two-gas methane using 0.1 Μ tetrabutylammonium hexafluorophosphate as a supporting electrolyte (scanning rate of 50 mV/s) using a platinum wire working electrode 'gold counter electrode and The Ag/AgCl reference electrode in 3 M KC1 149615.doc -67- 201111345 consists of a conventional three-electrode configuration to record β Ύ to convert the measured potential into SCE (saturated recording electrode) with ·4·4 eV Corresponding ionization from the initial oxidation-reduction potential relative to the energy level of the vacuum Bit (Ip) and electron affinity (EA) values (EA=E reduction start +4.4 eV, IP=Ea start +4 4 eV). Absorption spectra are used at concentrations ranging from 1·8χ1〇-6 to 3 1χ1 A two-gas ablation solution between 〇6 M (unless otherwise stated) was recorded on a Shimadzu UV-3101 PC UV-vis-NIR spectrophotometer. The following reaction scheme was synthesized to show the method for preparing the bipolar compound of the present invention. 149615.doc -68- 201111345
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亨'寸3^022 fvAE^O 欢緦嗜<πΝς#φ^·ς®^^ 149615.doc •73· 201111345 第i部分-中間體之合成 實例1-化合物A1之合成 向 4-氰基苯基硼酸(3.15 g,21.4 mmol) ' 9,9·二己基-2,7-二溴苐(21.14 g,43.0 mmol)及四(三苯基膦)鈀(0 495 g, 0.428 mmol、每個C-Br鍵為2%)之混合物中添加脫氣k2C03 水溶液(100 mL)及脫氣曱苯(150 mL)。在N2保護下將溶液 回流24 h »用CH/h (100 mLx4)萃取所得褐色溶液。合併 的有機層經MgSCU乾燥並在減壓下蒸發以去除溶劑。然後 利用矽膠管柱使用CP^Ch/己烷(1:2)作為洗脫液來純化殘 留物’獲得呈淺黃色固體形式之期望產物(7.40 g,產率為 67%)。4 NMR (400 MHz,CDC13): δ (ppm) 7.75-7.7.7 〇, 5H), 7.56-7.60 (m, 2H), 7.47-7.52 (m, 3H), 1.95-2.04 (m, 4H), 1.06-1.15 (m, 12H), 0.77 (t, 6H, J=7.6 Hz), 0.62-0.66 (m, 4H)。 實例2-化合物AS之合成 以與針對化合物A1所述相同之方式,使4-氰基苯基硼酸 (0.7 g,4.76 mmol)與二溴-第三(9,9-二己基)苐(11.0 g,9.52 mmol)反應,得到呈淺黃色固體形式之化合物a3(4 28 g, 產率為76%)。1HNMR(400 MHz,CDCl3):δ(ppm)7·58-7-83 (m, 20H), 7.47-7.49 (m, 2H), 1.98-2.13 (m, 12H), 1-09-1.15 (m,36 H),0.77-0.80 (m,30H)。 實例化合物C之合成 以與針對化合物A1所述相同之方式,使3-氰基苯基硼酸 (〇·8 g,4.76 mmol)與二溴 _ 第三(9,9-二己基)第(11.0 g,9.52 149615.doc •74· 201111345 mmol)反應,得到呈淺黃色固體形式之化合物c(4.28 g,產 率為 56%)。4 NMR (400 MHz, CDC13): δ (ppm) 7·96 (s, 1H), 7.91 (d, 1H, J=8.0 Hz), 7.74-7.84 (m, 6H), 7.54-7.70 (m, 12H), 7.47-7.49 (m, 1H), 7.31-7.38 (m, 1H), 1.97-2.11 (m,12H),1.09-1.12 (m,36H),0.77-0.80 (m, 30H)。 實例4-化合物B1之合成 向化合物 A1 (5.0 g,9.73 mmol)、雙(戊醯)二棚(3.70 g, 14.57 mmol)、二氣[1,Γ-雙(二苯基膦基)二茂鐵]鈀(240 mg, 0.29 mmol,每個C-Br 鍵為 3%)及乙酸鉀(1.72 g,17.53 mmol)之混合物中添加脫氣1,4-二噁院(1〇〇 mL)。將溶液在 80°C下加熱3 h。然後用CH2C12(50 mLx4)萃取溶液。合併 的有機層經MgS04乾燥並在減壓下蒸發以去除溶劑。然後 利用矽膠管柱使用CHzCl2/己烷(1:2)作為洗脫液來純化殘 留物,獲得呈淺黃色固體形式之期望產物(5.1 6 g,產率為 95%)。咕 NMR (400 MHz,CDC13): δ (ppm) 7.79-7.84 (m, 2H), 7.72-7.77 (m, 6H), 7.57 (d, 1H, J=8.0 Hz), 7.53 (s, 1H), 1.99-2.08 (m, 4H), 1.39 (s, 12H), 1.02-1.11 (m, 12H), 0.74 (t, 6H,J=7.6 Hz), 0.59-0.66 (m, 4H)。 實例5 -化合物B 3之合成 以與針對化合物B1所述相同之方式,使化合物A3 (1.02 g,0.865 mmol)與雙(戊醯)二硼(0.263 g,1.04 mmol)反應, 得到呈淺黃色固體形式之化合物B3(0.639 g,產率為 60%)。】H NMR (400 MHz,CDC13): δ (ppm) 7.57-7.85 (m, 22H),2.05-2.14 (m,12H),1.39 (s,12H),1.05-1.12 (m, -75- 149615.doc c 201111345 36H),0.72-0.83 (m,30H)。 實例6-化合物d之合成 以與針對化合物B1所述相同之方式,使化合物C(0.6 g, 0.51 mmol)與雙(戊醯)二硼(0155 g,0.61 mmol)反應,得 到呈淺黃色固體形式之化合物D(0.39 g,產率為62%)。 NMR (400 MHz, CDC13): δ (ppm) Ί.96 (s, 1H), 7.91 (d, 1H, J=7.6 Hz), 7.78-7.84 (m, 7H), 7.74 (d, 1H, J=7.6 Hz), 7.54-7.70 (m, 12H), 2.04-2.11 (m, 12H), 1.40 (s, 12H), 1.07-1.12 (m,36H),0.70-0.82 (m,30H)。 第Π部分-雙極化合物之合成 實例Ί -化合物I之合成 向化合物 Bl(4.00 g,7.13 111111〇1)、4,4,,4,,-參(3,6-二溴吟 。坐基-Ο-基)-三苯基胺(1.15 g,0.95 mmol)及四(三苯基膦)把 (0_ 197 g,〇· 1 7 mmol,每個C-Br鍵為3%)之混合物中添加脫 氣K2C03水溶液(1〇〇 mL)及脫氣曱苯(150 mL)。在n2保護 下將溶液回流24 h。用CHbChUOO mLx4)萃取所得褐色溶 液。合併的有機層經MgS〇4乾燥並在減壓下蒸發以去除溶 劑。然後利用矽膠管柱使用CH2C12/己烷(8:1)作為洗脫液 來純化殘留物,獲得呈淺黃色固體形式之期望產物〇91 g,產率為 62%)。NMR (400 MHz,CD2C12): δ (ppm) 8.62 (s, 6H), 7.66-7.92 (m, 84H), 2.10-2.21 (m, 24H), 1.06-1.16 (m,72H),0.75-0.80 (m,60H),MS (MALDI): m/z=334i.99 (C246H246N10 之計算值:3342.65)。HOMO : -5.17 eV, LUMO : -2.02 eV。於曱苯溶液中之量子效率:0.74。 149615.doc -76· 201111345 實例化合物2之合成 以與針對化合物1所述相同之方式,使化合物B3(〇 632 g,0.515 mmol)與 4,4',4"-參(3,6-二溴吁 „坐基 基)·三苯基 胺(0.083 g,0.069 mmol)反應,得到呈白色固體形式之化 合物 2(0.305 g,產率為 58%)。NMR (400 MHz,CD2C12): δ (ppm) 8.66 (s,6H),7.72-7.94 (m, i44H),7.66 (d,12H, J=7.6 Hz), 2.13-2.20 (m, 72H), 1.11-1.20 (m, 216H), 0.76- 0.83 (m,180H),MS (MALDI) : m/z=7733.63(C546H630N10 之計算值:7732.91)。HOMO : -5.17 eV,LUMO : -2.13 eV。於甲苯溶液中之量子效率:0.72。 實例9 -化合物J之合成 以與針對化合物1所述相同之方式,使化合物D(〇.318 g, 0.25 9 mmol)與4,4',4Π-參(3,6-二溴咔唑基-〇_基三苯基胺 (0.03 5 g,0.029 mmol)反應,得到呈白色固體形式之化合 物 3(0.152 g ’ 產率為 72%)。4 NMR (400 MHz,CD2C12): δ (ppm) 8.66 (s, 6H), 8.02 (s, 6H), 7.86-7.97 (m, 60H), 7.60-7.81 (m, 90H), 2.13-2.20 (m, 72H), 1.11-1.19 (m, 216H), 0.76-0.83 (m, 180H) > MS (MALDI) : m/z=7333.65 (C546H63〇N丨。之計算值:7332.91)。HOMO : -5.16 eV, LUMO : -2.09 eV。於曱苯溶液中之量子效率:0.65。 實例10-化合物4之合成 向化合物 A3(0.537 g,0.455 mmol)、聯苯胺(17 mg, 0.092 mmol)、乙酸鈀(6 mg, 0.027 mmo 卜每個 C-Br 鍵為 5%)及1,Γ-雙(二苯基膦基)二茂鐵(27 mg, 0.048 mmol)之混 149615.doc •77· 201111345 合物中添加25 mL脫氣無水甲苯。將溶液在95°C下加熱2 天。然後用CH2C12(30 mL><4)萃取溶液。合併的有機層經 MgS〇4乾燥並在減壓下蒸發以去除溶劑。然後利用石夕膠管 柱使用CHaClz/己烷(1.5:1)、然後使用乙酸乙酯/己烷(1:4) 作為洗脫液來純化殘留物’獲得呈淺黃色固體形式之期望 產物(0.153 g,產率為 36%)。4 NMR (400 MHz,CD2C12): δ (ppm) 7.57-7.83 (m,80 H),7.58 (d,4H, J=8.4 Hz),7.33 (s, 4H), 7.28 (d, 4H, J=8.4 Hz), 7.16 (d, 4H, J=8.4 Hz), 1.99-2.14 (m, 48H), 1.11-1.24 (m, 144H), 0.80-0.86 (m, 120H),MS (MALDI) : m/z=4578.92(C34〇H4〇8N6 之計算 值:4579.08)。HOMO : -4·97 eV ’ LUMO : -2.15 eV。存 於曱苯溶液中之量子效率:0.4i。 實例11 - 2-溴-9,9-二己基第之合成 將9.8 g 2-溴苐、39.6 g 1-溴己烷、2·58 g四丁基溴化銨 及75 ml 50% NaOH添加至250 ml圓底燒瓶中。將混合物授 拌並加熱至80°C,過夜。分離出有機層並用醚萃取水相。 將有機層用鹽水洗滌,並用無水MgS〇4乾燥。蒸發溶劑並 使殘留物經過短矽膠管柱,得到15.45 g產物(93 8%)。 實例12- 2-漠-Ί-确基>二己基葬之合成 將 7.0g2-溴-9,9·二己基第、56.6ml 乙酸及 3 39 ml 1〇〇% HN〇3混合物攪拌2小時,然後倒入大量的冰水,用Na2C〇3 粉末鹼化,直至PH>7為止,藉由乙酸乙酯萃取。將有機層 用鹽水洗滌,並用無水MgS〇4乾燥。蒸發溶劑並使殘留物 經過矽膠管柱,得到4.91 g 2-溴-7-硝基_9,9_二己基第 149615.doc -78 - 201111345 (63.2%)。 實例IS- 2-胺基-Ί-溴-9,9-二己基葬之合成 在攪拌下將2.6 g Zn粉末小心地逐漸添加至1〇 mi 2_漠_ 7:硝基-9,9-二己基苐、20 ml濃HC1及50 ml乙醇之混合物 中。將混合物回流半小時。冷卻後,藉由醚萃取混合物。 將有機層用鹽水洗滌,並用無水MgSCU乾燥。蒸發溶劑並 使殘留物經過矽膠管柱,得到3·42 g 2-胺基-7-溴-9,9-二己 基舞(80.1%)。 實例14- NW-參(Ί-溴-9,9-二己基$-7-基)胺之合成 在N2氣氛下將2.14 g 2-胺基-7-溴-9,9-二己基苐、0.72 Ο 氧化亞銅⑴及10.78 g 2-溴-9,9-二己基-7-碘-9H-g於1_笨 氧基苯中之混合物在油浴中加熱至220°c,並保持24小 時。將反應混合物冷卻至室溫且然後過濾以去除過量的鋼 錯合物。將濾液蒸發至乾燥並使其經過矽膠管柱,得到 3.13 g產物(50%)。 實例15 -化合物5之合成 將 0.126 g N,N,N-參(7-溴-9,9-二己基苐-7-基)胺、〇.〇88 g 4-氰基苯基硼酸及3.4 mg四(三苯基膦)鈀之混合物添加至 甲苯(15 mL)與2 Μ無水Na2C03溶液(12 mL)之無空氣兩相 混合物中。在氬氣氛及11 〇°C下將所得混合物劇烈攪拌24 小時。分離出有機層並用醚萃取水相。將有機層用鹽水 (2x50 mL)洗滌,並用無水MgS〇4乾燥。蒸發溶劑並使殘 留物經過矽膠管柱。藉由在庚烷中重結晶獲得純淨化合物 5,得到 0.096 g 化合物 5(71%)。NMR (4〇〇 MHz, 149615.doc -79- 201111345 CDC13): δ (ppm) 7.756-7.525 (m,24H),7.40-7.20(與 CHC13 重疊,3H),(s,3H),2.013-1.865 (m,12H),1.227-1.135 (m, 36H),0.815-0.697 (m,30H)。MS (MALDI-TOF) : m/z=1318.01 (C96H1()8N4之計算值:1317.86)。分析實驗值:c, 87.52; H,8.25; N, 4.29(計算值:C,87.49; H,8.26; N,4.25)。 HPLC : 99.87%。 第III部分·裝置製作及量測 實例16-具有Vr〇/PEDOT:PSS/化合物1/TPBl/LiF/Al構型之 OLED裝置之製作 將30 mg化合物1溶於4 ml氯仿中並藉助〇.2 mm PTFE過 濾器過濾以供裝置製作用。發光裝置係在經圖案化氧化銦 錫(ITO)塗佈之玻璃基板上製備。清潔基板並用氧電漿處 理並經旋塗以具有45 nm摻雜有聚(苯乙烯磺酸)(pSS)之聚 (3,4-伸乙基二氧基噻吩)(?£〇〇!'),隨後在120。(:下在空氣 中乾燥1 5 min。將聚合物溶液旋塗以形成厚度為約4〇 nm 之發射層並轉移至處於1x1 Ο·5 Pa真空下之室中。在發射層 表面上沈積25 nm 1,3,5-參(苯基-2-苯并。米唾基)苯(TPBI)以 供電子注入及電洞阻檔用。陰極由依序經熱沈積之〇 5 nm LiF及150 nm A1組成。所有量測均係在空氣中在室溫下實 施。使用Keithley 2420源表及校準光二極體記錄裝置之電 流-電壓、電流-發光特性。利用〇cean 〇ptics USB2000小 型光纖光s普儀§己錄EL光谱。使用該裝置之電流_電壓-發光 數據及EL光譜計算測光度數據。裝置之導通電壓為3.$亨' inch 3^022 fvAE^O 缌 缌 <πΝς#φ^·ς®^^ 149615.doc •73· 201111345 Part I - Synthesis of intermediates Example 1 - Synthesis of compound A1 to 4-cyano Phenylboronic acid (3.15 g, 21.4 mmol) '9,9·dihexyl-2,7-dibromofluorene (21.14 g, 43.0 mmol) and tetrakis(triphenylphosphine)palladium (0 495 g, 0.428 mmol, per A mixture of degassed k2C03 (100 mL) and degassed benzene (150 mL) were added to a mixture of 2% C-Br. The solution was refluxed for 24 h under N2. <<>>> The combined organic layers were dried over Mg SCU and evaporated under reduced pressure to remove solvent. The residue was then purified using a <RTI ID=0.0></RTI> <RTI ID=0.0></RTI> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; 4 NMR (400 MHz, CDC13): δ (ppm) 7.75-7.7.7 〇, 5H), 7.56-7.60 (m, 2H), 7.47-7.52 (m, 3H), 1.95-2.04 (m, 4H), 1.06-1.15 (m, 12H), 0.77 (t, 6H, J = 7.6 Hz), 0.62-0.66 (m, 4H). Example 2 - Synthesis of Compound AS 4-cyanophenylboronic acid (0.7 g, 4.76 mmol) and dibromo-tris(9,9-dihexyl)anthracene (11.0) in the same manner as described for compound A1. g, 9.52 mmol) gave compound a3 (428 g, yield 76%) as a pale yellow solid. 1H NMR (400 MHz, CDCl3): δ (ppm) 7·58-7-83 (m, 20H), 7.47-7.49 (m, 2H), 1.98-2.13 (m, 12H), 1-09-1.15 (m , 36 H), 0.77-0.80 (m, 30H). Synthesis of Example Compound C In the same manner as described for Compound A1, 3-cyanophenylboronic acid (〇·8 g, 4.76 mmol) and dibromo- 3 (9,9-dihexyl) (11.0) g, 9.52 149615.doc • 74· 201111345 mmol) gave compound c (4.28 g, yield 56%) as a pale yellow solid. 4 NMR (400 MHz, CDC13): δ (ppm) 7·96 (s, 1H), 7.91 (d, 1H, J=8.0 Hz), 7.74-7.84 (m, 6H), 7.54-7.70 (m, 12H ), 7.47-7.49 (m, 1H), 7.31-7.38 (m, 1H), 1.97-2.11 (m, 12H), 1.09-1.12 (m, 36H), 0.77-0.80 (m, 30H). Example 4 - Synthesis of Compound Bl to Compound A1 (5.0 g, 9.73 mmol), bis(pentanyl) shed (3.70 g, 14.57 mmol), diox [1, fluorene-bis(diphenylphosphino) dioxin Degassed 1,4-dioxin (1 〇〇 mL) was added to a mixture of iron]palladium (240 mg, 0.29 mmol, 3% per C-Br bond) and potassium acetate (1.72 g, 17.53 mmol). The solution was heated at 80 ° C for 3 h. The solution was then extracted with CH2C12 (50 mL x 4). The combined organic layers were dried over MgSO 4 and evaporated under reduced pressure to remove solvent. The residue was purified using a EtOAc EtOAc EtOAc (EtOAc:EtOAc)咕NMR (400 MHz, CDC13): δ (ppm) 7.79-7.84 (m, 2H), 7.72-7.77 (m, 6H), 7.57 (d, 1H, J=8.0 Hz), 7.53 (s, 1H), 1.99-2.08 (m, 4H), 1.39 (s, 12H), 1.02-1.11 (m, 12H), 0.74 (t, 6H, J = 7.6 Hz), 0.59-0.66 (m, 4H). Example 5 - Synthesis of Compound B3 Compound A3 (1.02 g, 0.865 mmol) was reacted with bis(pentamidine)diboron (0.263 g, 1.04 mmol) in the same manner as described for compound B1 to give a pale yellow. Compound B3 (0.639 g, yield 60%) was obtained as a solid. H NMR (400 MHz, CDC13): δ (ppm) 7.57-7.85 (m, 22H), 2.05-2.14 (m, 12H), 1.39 (s, 12H), 1.05-1.12 (m, -75- 149615. Doc c 201111345 36H), 0.72-0.83 (m, 30H). Example 6 - Synthesis of compound d Compound C (0.6 g, 0.51 mmol) was reacted with bis(pentamethyl)diboron (0155 g, 0.61 mmol) in the same manner as described for compound B1 to give a pale yellow solid. Form Compound D (0.39 g, yield 62%). NMR (400 MHz, CDC13): δ (ppm) Ί.96 (s, 1H), 7.91 (d, 1H, J=7.6 Hz), 7.78-7.84 (m, 7H), 7.74 (d, 1H, J= 7.6 Hz), 7.54-7.70 (m, 12H), 2.04-2.11 (m, 12H), 1.40 (s, 12H), 1.07-1.12 (m, 36H), 0.70-0.82 (m, 30H). Part I - Synthesis of Bipolar Compounds Ί - Synthesis of Compound I to Compound Bl (4.00 g, 7.13 111111〇1), 4,4,,4,,-(3,6-dibromofluorene. -Ο-yl)-triphenylamine (1.15 g, 0.95 mmol) and tetrakis(triphenylphosphine) in a mixture of (0_197 g, 〇·17 mmol, 3% per C-Br bond) A degassed K2C03 aqueous solution (1 mL) and degassed benzene (150 mL) were added. The solution was refluxed for 24 h under n2 protection. The resulting brown solution was extracted with CHbChUOO mL x 4). The combined organic layers were dried over MgSO 4 and evaporated under reduced pressure to remove solvent. The residue was purified using a silica gel column using CH2C12 / hexanes (8:1) as eluent to afford desired product (yel. NMR (400 MHz, CD2C12): δ (ppm) 8.62 (s, 6H), 7.66-7.92 (m, 84H), 2.10-2.21 (m, 24H), 1.06-1.16 (m, 72H), 0.75-0.80 ( m, 60H), MS (MALDI): m/z = 334i.99 (calc. for C246H246N10: 3342.65). HOMO : -5.17 eV, LUMO : -2.02 eV. The quantum efficiency in the benzene solution was 0.74. 149615.doc -76· 201111345 Synthesis of Example Compound 2 In the same manner as described for Compound 1, Compound B3 (〇632 g, 0.515 mmol) and 4,4',4"-parameter (3,6-di) Reaction of bromo-p-(trimyl)-triphenylamine (0.083 g, 0.069 mmol) gave Compound 2 (0.305 g, yield: 58%) as a white solid. NMR (400 MHz, CD2C12): δ ( Ppm) 8.66 (s, 6H), 7.72-7.94 (m, i44H), 7.66 (d, 12H, J = 7.6 Hz), 2.13-2.20 (m, 72H), 1.11-1.20 (m, 216H), 0.76- 0.83 (m, 180H), MS (MALDI): m/z =7733.63 (calculated for C546H630N10: 7732.91). HOMO: -5.17 eV, LUMO: -2.13 eV. Quantum efficiency in toluene solution: 0.72. - Synthesis of Compound J In the same manner as described for Compound 1, Compound D (〇.318 g, 0.25 9 mmol) and 4,4',4Π-gin (3,6-dibromooxazolyl-oxime) were obtained. Reaction of _triphenylamine (0.03 5 g, 0.029 mmol) gave Compound 3 as a white solid (yield: 72%). NMR (400 MHz, CD2C12): δ (ppm) 8.66 ( s, 6H), 8.02 (s, 6H), 7.86-7.97 (m, 60H), 7.60-7.81 (m, 90H), 2. 13-2.20 (m, 72H), 1.11-1.19 (m, 216H), 0.76-0.83 (m, 180H) > MS (MALDI) : m/z =7333.65 (C546H63〇N丨. Calculated value: 7332.91) HOMO: -5.16 eV, LUMO: -2.09 eV. Quantum efficiency in benzene solution: 0.65. Example 10 - Synthesis of compound 4 to compound A3 (0.537 g, 0.455 mmol), benzidine (17 mg, 0.092 mmol) ), palladium acetate (6 mg, 0.027 mmo 5% per C-Br bond) and 1, bis-bis(diphenylphosphino)ferrocene (27 mg, 0.048 mmol) mixed 149615.doc • 77· 201111345 Add 25 mL of degassed anhydrous toluene. The solution was heated at 95 ° C for 2 days. The solution was then extracted with CH2C12 (30 mL >< 4). The combined organic layers were dried over MgSO.sub.4 and evaporated under reduced pressure to remove solvent. The residue was then purified using a mixture of CH.sub.2Cl.sub.2/. g, yield 36%). 4 NMR (400 MHz, CD2C12): δ (ppm) 7.57-7.83 (m, 80 H), 7.58 (d, 4H, J = 8.4 Hz), 7.33 (s, 4H), 7.28 (d, 4H, J= 8.4 Hz), 7.16 (d, 4H, J=8.4 Hz), 1.99-2.14 (m, 48H), 1.11-1.24 (m, 144H), 0.80-0.86 (m, 120H), MS (MALDI) : m/ z=4578.92 (calculated value of C34〇H4〇8N6: 4579.08). HOMO : -4·97 eV ’ LUMO : -2.15 eV. Quantum efficiency in a solution of toluene: 0.4i. Example 11 - Synthesis of 2-bromo-9,9-dihexyl No. 9.8 g of 2-bromoindole, 39.6 g of 1-bromohexane, 2.58 g of tetrabutylammonium bromide and 75 ml of 50% NaOH were added to In a 250 ml round bottom flask. The mixture was stirred and heated to 80 ° C overnight. The organic layer was separated and the aqueous phase was extracted with ether. The organic layer was washed with brine and dried over anhydrous MgSO4. The solvent was evaporated and the residue was applied to a pad of EtOAc to afford 15.45 g of product (93 8%). Example 12 - 2-Moisture-Ί-Accord> Synthesis of Dihexyl Fungus Stir a mixture of 7.0 g of 2-bromo-9,9·dihexyl, 56.6 ml of acetic acid and 3 39 ml of 1% HN〇3 for 2 hours. Then, a large amount of ice water was poured, and alkalized with Na2C〇3 powder until pH >7, and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous MgSO. The solvent was evaporated and the residue was applied to a silica gel column to afford 4.91 g of 2-bromo-7-nitro-9,9-dihexyl 149615.doc -78 - 201111345 (63.2%). Example IS-2 2-Amino-indole-bromo-9,9-dihexyl burial synthesis 2.6 g of Zn powder was carefully added gradually to 1 〇mi 2_ desert _ 7: nitro-9,9- with stirring A mixture of dihexyl hydrazine, 20 ml of concentrated HCl and 50 ml of ethanol. The mixture was refluxed for half an hour. After cooling, the mixture was extracted by ether. The organic layer was washed with brine and dried over anhydrous EtOAc. The solvent was evaporated and the residue was applied to a silica gel column to give 3·42 g of 2-amino-7-bromo-9,9-dihexyl (80.1%). Example 14 - Synthesis of NW-Find (Ί-bromo-9,9-dihexyl$-7-yl)amine 2.14 g of 2-amino-7-bromo-9,9-dihexylfluorene under N2 atmosphere. a mixture of 0.72 氧化 cuprous oxide (1) and 10.78 g of 2-bromo-9,9-dihexyl-7-iodo-9H-g in 1-phenyloxybenzene was heated to 220 ° C in an oil bath and kept at 24 hour. The reaction mixture was cooled to room temperature and then filtered to remove excess steel complex. The filtrate was evaporated to dryness and passed through a sep. column to afford 3.13 g (50%). Example 15 - Synthesis of Compound 5 0.126 g of N,N,N-parade (7-bromo-9,9-dihexylindol-7-yl)amine, 〇.〇88 g 4-cyanophenylboronic acid and 3.4 A mixture of mg tetrakis(triphenylphosphine)palladium was added to an airless two-phase mixture of toluene (15 mL) and 2 mL of anhydrous Na2CO3 solution (12 mL). The resulting mixture was vigorously stirred under an argon atmosphere at 11 ° C for 24 hours. The organic layer was separated and the aqueous phase was extracted with ether. The organic layer was washed with brine (2×50 mL) and dried over anhydrous EtOAc. The solvent was evaporated and the residue was passed through a cartridge column. Pure compound 5 was obtained by recrystallization from heptane to give 0.096 g of Compound 5 (71%). NMR (4〇〇MHz, 149615.doc -79- 201111345 CDC13): δ (ppm) 7.756-7.525 (m, 24H), 7.40-7.20 (overlap with CHC13, 3H), (s, 3H), 2.013-1.865 (m, 12H), 1.227-1.135 (m, 36H), 0.815-0.697 (m, 30H). MS (MALDI-TOF): m/z = 1318.01 (calc. for C96H1() 8N4: 1317.86). Found: c, 87.52; H, 8.25; N, 4.29 (calc.: C, 87.49; H, 8.26; N, 4.25). HPLC: 99.87%. Part III. Device fabrication and measurement Example 16 - Fabrication of an OLED device with Vr〇/PEDOT:PSS/Compound 1/TPB1/LiF/Al configuration 30 mg of Compound 1 was dissolved in 4 ml of chloroform with the aid of ruthenium. A 2 mm PTFE filter is filtered for the device. The light-emitting device was prepared on a patterned indium tin oxide (ITO) coated glass substrate. The substrate was cleaned and treated with oxygen plasma and spin coated to have poly(3,4-extended ethyldioxythiophene) doped with poly(styrenesulfonic acid) (pSS) at 45 nm (? ), then at 120. (: drying in air for 15 min. The polymer solution was spin coated to form an emissive layer having a thickness of about 4 〇 nm and transferred to a chamber at a vacuum of 1 x 1 Ο·5 Pa. Depositing on the surface of the emissive layer 25 Nm 1,3,5-parade (phenyl-2-benzo-mialyl)benzene (TPBI) for electron injection and hole block. The cathode is thermally deposited by 〇5 nm LiF and 150 nm. A1 composition. All measurements are carried out in air at room temperature. Use the Keithley 2420 source meter and calibrate the current-voltage, current-luminous characteristics of the photodiode recording device. Utilize 〇cean 〇ptics USB2000 small fiber optic light The instrument § has recorded the EL spectrum. The current-voltage-luminescence data and the EL spectrum of the device are used to calculate the photometric data. The turn-on voltage of the device is 3.
V。最大亮度為 4627 cd/m2。在 3700 Cd/m2 (9.5 V)下在 CIE 149615.doc •80 201111345 坐標為(0_16,0.14)時最大電流效率為1.44(;(1/八。1_¥丄特 性及電流效率對電壓之曲線圖解說明於圖6及圖7中。 t ///1 7- β- ^ITO/PEDOT:PSS/Yt ^ # 1 (4%) + CBP/TPBI/L iF/A l 構型之OLED裝置之製作 將1.2 mg化合物1及28.8 mg CBP溶於4 ml氣仿中並藉助 0.45 μιη PTFE過濾器過濾以供裝置製作用。發光裝置係在 經圖案化氧化銦錫(ΙΤΟ)塗佈之玻璃基板上製備。清潔基 板並用氧電浆處理並經旋塗以具有45 nm摻雜有聚(苯乙稀 確酸)(PSS)之聚(3,4-伸乙基二氧基。塞吩)(1>£[)〇1),隨後在 120C下在空氣中乾燥15 min。將發光分子溶液旋塗以形 成厚度為約40 nm之發射層並轉移至處於1 χίο·5 pa真空下 之室中。在發射層表面上沈積25 nm 1,3,5-參(苯基-2-苯并 咪唑基)苯(TPBI)以供電子注入及電洞阻擋用。陰極由依序 經熱沈積之0.5 nm LiF及150 nm A1組成。裝置之導通電壓 為5.5 V。最大免度為5630 cd/m2。在 534 cd/m2 (8.5 V)下 在CIE坐標為(0.15,〇·〇8)時最大電流效率為2.83 cd/A。I- V-L特性及電流效率對電壓之曲線圖解說明於圖6及圖7 中。 結果及分析 表1顯不自化合物1、化合物2及揭示於W〇2〇〇8/〇69756A1 中之比較化合物A及b在曱苯中之uv及PL光譜所獲得之值 之比較。 包含電洞傳輸核心及3個或更多個周圍臂取代基之實例 與其他具有更少臂之雙極化合物相比具有更小之偶極矩 149615.doc • 81· 201111345 (為進行比較,將W02008/069756A1之化合物A及B報告於1 中)。表1顯示本發明中所揭示化合物(化合物1及2)與 W02008/009750A1之雙極化合物之間計算偶極矩之比較。 當化學結構由兩個不對稱臂向六個對稱臂變化時,四種化 合物在曱苯溶液中之UV及PL量測顯示吸收光譜及發射光 譜二者均明顯藍移。 化合物 化學結構 偶極矩 UV Xmax (nm) (溶劑) PL λΠΊ3Χ (nm) A nc{)~O^Oj^O^O~<IVcn Hl3〇6 CeH-13 f|l H13C6 〇6Hl3 (io 4.564 384 442 B Η·ι3〇6 〇θΗΐ3 f^ll ^13〇6 〇βΗΐ3 (ίο 0.838 378 432 1 Η:>ο NC - 3.058 355 409 149615.doc -82- 201111345V. The maximum brightness is 4627 cd/m2. At 3700 Cd/m2 (9.5 V) in CIE 149615.doc •80 201111345 The coordinates are (0_16, 0.14) and the maximum current efficiency is 1.44 (; (1/1. 1_¥丄 characteristic and current efficiency versus voltage curve) This is illustrated in Figure 6 and Figure 7. t ///1 7- β- ^ITO/PEDOT:PSS/Yt ^ # 1 (4%) + CBP/TPBI/L iF/A l OLED device fabrication 1.2 mg of Compound 1 and 28.8 mg of CBP were dissolved in 4 ml of gas and filtered through a 0.45 μηη PTFE filter for fabrication. The luminescent device was prepared on a patterned indium tin oxide (yttrium) coated glass substrate. The substrate was cleaned and treated with oxygen plasma and spin coated to have a poly(3,4-extended ethyldioxy group) having a 45 nm doped poly(styrene) (PSS) (1> £[)〇1), followed by drying in air at 120 C for 15 min. The luminescent molecular solution was spin coated to form an emissive layer having a thickness of about 40 nm and transferred to a chamber at 1 χίο·5 pa vacuum. 25 nm 1,3,5-parade (phenyl-2-benzimidazolyl)benzene (TPBI) was deposited on the surface of the emissive layer for electron injection and hole blocking. The cathode was thermally deposited by 0.5 nm LiF and 150 nm A1 consisting of a device with a turn-on voltage of 5.5 V. The maximum immunity is 5630 cd/m2. At 534 cd/m2 (8.5 V), the maximum current efficiency is 2.83 cd at a CIE coordinate of (0.15, 〇·〇8). A. I-VL characteristics and current efficiency versus voltage curves are illustrated in Figures 6 and 7. Results and Analysis Table 1 is not shown in Compound 1, Compound 2 and is disclosed in W〇2〇〇8/〇69756A1 Comparison of the values obtained for the uv and PL spectra of compounds A and b in toluene. Examples of hole transport cores and 3 or more surrounding arm substituents and other bipolar compounds with fewer arms Than having a smaller dipole moment 149615.doc • 81· 201111345 (for comparison, compounds A and B of W02008/069756A1 are reported in 1). Table 1 shows the compounds disclosed in the present invention (Compounds 1 and 2) Calculation of the dipole moment between the bipolar compounds of W02008/009750A1. When the chemical structure changes from two asymmetric arms to six symmetric arms, the UV and PL measurements of the four compounds in the benzene solution show absorption. Both the spectrum and the emission spectrum are significantly blue-shifted. UV Xmax (nm) (solvent) PL λΠΊ3Χ (nm) A nc{)~O^Oj^O^O~<IVcn Hl3〇6 CeH-13 f|l H13C6 〇6Hl3 (io 4.564 384 442 B Η·ι3 〇6 〇θΗΐ3 f^ll ^13〇6 〇βΗΐ3 (ίο 0.838 378 432 1 Η:>ο NC - 3.058 355 409 149615.doc -82- 201111345
中。 在圖4中將化合物1及化合物2之UV光譜與化合物A及B之 光譜進行比較。 在圖5中將化合物1及化合物2之pL光譜與比較化合物a 及B之光譜進行比較。因提供具有化合物1及2之多臂結構 之化合物致使光譜向較低波長顯著移動。實際上,具支鏈 多臂結構允許發射波長具有相當大的撓性:藉由適當調節 分佈於多個臂中之發射部分,可達成波長之「調整」。 使用存於CBP中之4%化合物1及純淨化合物丨作為發射層 之OLED裝置之I-V-L特性示於圖6中。 自使用存於CBP中之4%化合物1及純淨化合物丨作為發射 層之OLED裝置獲得之電流效率對電壓之曲線示於圖7中。 最大電流交文率為2.83尤佳,《其在與深M色發射(對應於顏 色坐標0.15, 0.08)組合時。 149615.doc -83- 201111345 【圖式簡單說明】 圖1顯示本文所述化合物之示意圖; 圖2顯示化合物1至4之uv光譜; 圖3顯示化合物!至4在曱苯中之光致發光(pL)光譜; 圖4顯示化合物丨、化合物2及比較化合物八及B在甲笨中 之UV光譜; 圖5顯示化合物1、化合物2及比較化合物a及B在曱笨中 之PL光譜; 圖6顯示使用存於CBP中之4%化合物1及純淨化合物1作 為發射層之OLED裝置之I-V-L特性;及 圖7顯示使用存於CBP中之4%化合物1及純淨化合物1作 為發射層之OLED裝置之電流效率與電壓之關係曲線。 【主要元件符號說明】 1〇 化合物 12 核心部分 14、16、1 8 臂 2〇 缺電子部分 22 發射部分 1496I5.doc -84-in. The UV spectra of Compound 1 and Compound 2 were compared with the spectra of Compounds A and B in Figure 4. The pL spectra of Compound 1 and Compound 2 were compared with the spectra of Comparative Compounds a and B in Figure 5. Since the compound having the multi-arm structure of Compounds 1 and 2 is provided, the spectrum is significantly shifted toward lower wavelengths. In fact, the branched multi-arm structure allows for a considerable degree of flexibility in the emission wavelength: the "adjustment" of the wavelength can be achieved by appropriately adjusting the emission portions distributed in the plurality of arms. The I-V-L characteristics of the OLED device using 4% of the compound 1 and the neat compound 丨 as the emission layer in CBP are shown in Fig. 6. The current efficiency vs. voltage curve obtained from an OLED device using 4% of Compound 1 and a pure compound 存 as an emission layer in CBP is shown in Fig. 7. The maximum current cross rate is preferably 2.83, which is combined with deep M color emission (corresponding to color coordinates of 0.15, 0.08). 149615.doc -83- 201111345 [Simplified Schematic] Figure 1 shows a schematic of the compounds described herein; Figure 2 shows the uv spectrum of compounds 1 to 4; Figure 3 shows compounds! Photoluminescence (pL) spectrum of benzene in benzene; Figure 4 shows the UV spectrum of compound hydrazine, compound 2 and comparative compounds VIII and B in methacrylate; Figure 5 shows compound 1, compound 2 and comparative compound a and B spectrum of B in sputum; Figure 6 shows the IVL characteristics of an OLED device using 4% of Compound 1 and Pure Compound 1 as CPA in CBP; and Figure 7 shows the use of 4% of Compound 1 in CBP And the current efficiency versus voltage curve of the OLED device with pure compound 1 as the emissive layer. [Explanation of main component symbols] 1〇 Compound 12 Core part 14, 16, 1 8 arm 2〇 Electron-deficient part 22 Emission part 1496I5.doc -84-
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