TW201928006A - Quinoline-substituted diphenylpyrimidines compounds and organic electroluminescent devices using the same - Google Patents
Quinoline-substituted diphenylpyrimidines compounds and organic electroluminescent devices using the same Download PDFInfo
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本發明係關於一種用於有機電激發光元件之材料及使用該材料之有機電激發光元件,尤係關於一種可增加元件效率與延長有機電激發光元件壽命之材料及使用該材料之有機電激發光元件。 The present invention relates to a material for an organic electroluminescent device and an organic electroluminescent device using the same, and more particularly to a material which can increase the efficiency of the device and prolong the life of the organic electroluminescent device and the organic device using the material. Excitation light element.
近來,有機電激發光元件(OLED)在高發光率的高密度畫素顯示器上因具備長壽命、高效率、低驅動電壓、色域廣及成本低等優勢,而具有商業性吸引力,為滿足該有機電激發光元件之應用,特別著重其新穎的有機材料之開發。 Recently, organic electroluminescent devices (OLEDs) have commercial advantages due to their long life, high efficiency, low driving voltage, wide color gamut, and low cost on high-luminance high-density pixel displays. It satisfies the application of the organic electroluminescent device, with particular emphasis on the development of its novel organic materials.
典型的OLED至少一夾置於陽極與陰極間之有機發光層(organic emissive)層。當施加電流時,陽極注入電洞且陰極注入電子至該一層或多層有機發光層,被注入的電洞及電子各自遷移至相反的帶電荷電極。當電子及電洞侷限在相同的分子上時,形成”激子(exciton)”,該激子係具有受激發能態的侷限化電子-電洞對,通過發光機制,該激 子鬆弛而發射光。為求提升此等元件的電荷傳輸能力及發光效率,於發光層旁結合一層或多層之額外層體,例如電子傳輸層及/或電洞傳輸層,或電子阻擋層及/或電洞阻擋層。文獻中,已充分證明在主體材料摻混另一客體材料,以提升裝置性能及調整色度。全文併入本文參考的第4769292、5844363、5707745、6596415及6465115號美國專利中敘述了幾種OLED材料和裝置組構。昱鐳光電科技已經在2016年申請並於2017年獲證中華民國專利號I582081,此專利所介紹的電子傳輸材料已經具有一定的新穎性與效果,而本新申請專利的效果更勝於此前案。 A typical OLED is sandwiched between at least one organic emissive layer between the anode and the cathode. When a current is applied, the anode is injected into the hole and the cathode injects electrons into the one or more organic light-emitting layers, and the injected holes and electrons each migrate to the opposite charged electrode. When electrons and holes are confined to the same molecule, an "exciton" is formed, which has a localized electron-hole pair excited by an excited energy state, which is excited by a luminescence mechanism. The child relaxes and emits light. In order to improve the charge transport capability and luminous efficiency of such components, one or more additional layers, such as an electron transport layer and/or a hole transport layer, or an electron blocking layer and/or a hole blocking layer, are bonded adjacent to the light emitting layer. . In the literature, it has been well documented that the host material is blended with another guest material to enhance device performance and adjust color. Several OLED materials and device configurations are described in U.S. Patent Nos. 4,769,292, 5,844,363, 5,707,745, 6,,,,,, 6,昱Ray Optoelectronics Technology has applied for in 2016 and was awarded the Republic of China Patent No. I582081 in 2017. The electronic transmission materials introduced in this patent have certain novelty and effect, and the effect of this new patent application is better than the previous case. .
製造具多層薄膜結構OLED之原因包含使該等電極及有機層之間之界面安定及有機材料的搭配。在有機材料中,其電子及電洞之遷移率(mobility)明顯不同,若使用相稱之電洞傳輸及電子傳輸層,電洞及電子可有效地傳輸至該發射層,使該發射層中該電子及電洞之密度平衡,增加發光效率。適當之結合該上述有機層可增進該元件效率及壽命。然而,仍難以找到滿足所有實際顯示器應用之需求的有機材料,尤係用於車用顯示器或是照明光源之有機材料,需具備耐高溫與長壽命的性質。 The reason for manufacturing a multi-layer thin film structure OLED includes the stability of the interface between the electrodes and the organic layer and the combination of organic materials. In organic materials, the mobility of electrons and holes is significantly different. If a so-called hole transmission and electron transport layer is used, holes and electrons can be efficiently transmitted to the emissive layer, so that the emissive layer The density of electrons and holes is balanced to increase luminous efficiency. Properly combining the above organic layers enhances the efficiency and longevity of the component. However, it is still difficult to find organic materials that meet the needs of all practical display applications, especially organic materials for vehicle displays or illumination sources, which are required to have high temperature resistance and long life.
因此,亟需一種有機材料可顯著改善有機電激發光元件的壽命、提高載子遷移率及良好耐熱性,以符合多樣化應用的需求。 Therefore, there is a need for an organic material that can significantly improve the lifetime of the organic electroluminescent device, improve carrier mobility, and good heat resistance to meet the needs of diverse applications.
本發明之目的在於提供一種具有較長壽命、高載子遷 移率及耐熱性佳之用於有機電激發光元件之材料。 The object of the present invention is to provide a long life and high carrier A material for organic electroluminescent elements that has good mobility and heat resistance.
本發明提供一種具式(I)結構之經喹啉取代之二苯基嘧啶化合物:
其中,X1表示經取代或未經取代之C6-30芳基、經取代或未經取代之含有選自由N、O、及S所組成群組中之至少一雜原子之C5-30雜芳基;A1表示經取代或未經取代之C6-36芳基、經取代或未經取代之含有選自由N、O、及S所組成群組中之至少一雜原子之C5-30雜芳基;X1及A1為相同或相異,且至少有一個為經取代或未經取代之含有選自由N、O、及S所組成群組中之至少一雜原子之C5-30雜芳基;以及n表示1或2之整數,且當n表示2時,A1各自為相同或相異。 Wherein X 1 represents a substituted or unsubstituted C 6-30 aryl group, substituted or unsubstituted C 5-30 containing at least one hetero atom selected from the group consisting of N, O, and S; a heteroaryl group; A 1 represents a substituted or unsubstituted C 6-36 aryl group, substituted or unsubstituted C 5 containing at least one hetero atom selected from the group consisting of N, O, and S; -30heteroaryl ; X 1 and A 1 are the same or different, and at least one of them is substituted or unsubstituted, and contains at least one hetero atom selected from the group consisting of N, O, and S. 5-30heteroaryl ; and n represents an integer of 1 or 2, and when n represents 2, each of A 1 is the same or different.
本發明復提供一種有機電激發光元件,包含:陰極;陽極;以及有機層,係介於該陰極與陽極之間,且該有機層包含本發明之具式(I)結構之經喹啉取代之二苯基嘧啶化合物。 The present invention provides an organic electroluminescent device comprising: a cathode; an anode; and an organic layer interposed between the cathode and the anode, and the organic layer comprises a quinoline substitution of the structure of the formula (I) of the present invention Diphenylpyrimidine compound.
根據本發明,藉由本發明提供之具式(I)結構之經喹啉 取代之二苯基嘧啶化合物,可改善有機電激發光元件的壽命、提高載子遷移率及提供良好耐熱性的好處。 According to the present invention, the quinoline having the structure of formula (I) provided by the present invention The substituted diphenylpyrimidine compound can improve the life of the organic electroluminescent device, improve carrier mobility, and provide good heat resistance.
100、200、300‧‧‧有機電激發光元件 100, 200, 300‧‧‧ Organic electroluminescent components
110、210、310‧‧‧基板 110, 210, 310‧‧‧ substrates
120、220、320‧‧‧陽極 120, 220, 320‧‧‧ anode
130、230、330‧‧‧電洞注入層 130, 230, 330‧‧‧ hole injection layer
140、240、340‧‧‧電洞傳輸層 140, 240, 340‧‧‧ hole transport layer
150、250、350‧‧‧發光層 150, 250, 350‧‧ ‧ luminescent layer
160、260、360‧‧‧電子傳輸層 160, 260, 360‧‧‧ electron transport layer
170、270、370‧‧‧電子注入層 170, 270, 370‧‧‧ electron injection layer
180、280、380‧‧‧陰極 180, 280, 380‧‧‧ cathode
245、355‧‧‧激子阻擋層 245, 355‧‧ ‧ exciton blocking layer
透過例示性之參考附圖說明本發明的實施方式:第1圖係本發明之有機電激發光元件之一實施例之剖面示意圖;第2圖係本發明之有機電激發光元件之另一實施例之剖面示意圖;以及第3圖係本發明之有機電激發光元件之又一實施例之剖面示意圖。 Embodiments of the present invention are described with reference to the accompanying drawings in which: FIG. 1 is a schematic cross-sectional view showing an embodiment of an organic electroluminescent device of the present invention; and FIG. 2 is another embodiment of the organic electroluminescent device of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 3 is a schematic cross-sectional view showing still another embodiment of the organic electroluminescent device of the present invention.
以下係藉由特定的具體實施例說明本發明之實施方式,熟習此技藝之人士可由本說明書所揭示之內容輕易地瞭解本發明之優點及功效。本發明亦可藉由其它不同之實施方式加以施行或應用,本說明書中的各項細節亦可基於不同觀點與應用,在不悖離本發明所揭示之精神下賦予不同之修飾與變更。此外,本文所有範圍和值都係包含及可合併的。落在本文中所述的範圍內之任何數值或點,例如任何整數都可以作為最小值或最大值以導出下位範圍等。 The embodiments of the present invention are described by way of specific examples, and those skilled in the art can readily understand the advantages and functions of the present invention from the disclosure. The present invention may be embodied or applied by other different embodiments, and the various details of the present invention may be variously modified and changed without departing from the spirit and scope of the invention. In addition, all ranges and values herein are inclusive and combinable. Any value or point falling within the ranges recited herein, such as any integer, may be the minimum or maximum value to derive the lower range and the like.
依據本發明,一種具式(I)結構之經喹啉取代之二苯基嘧啶化合物:
其中,X1表示經取代或未經取代之C6-30芳基、經取代或未經取代之含有選自由N、O、及S所組成群組中之至少一雜原子之C5-30雜芳基;A1表示經取代或未經取代之C6-36芳基、經取代或未經取代之含有選自由N、O、及S所組成群組中之至少一雜原子之C5-30雜芳基;X1及A1為相同或相異,且至少有一個為經取代或未經取代之含有選自由N、O、及S所組成群組中之至少一雜原子之C5-30雜芳基;以及n表示1或2之整數,且當n表示2時,A1各自為相同或相異。 Wherein X 1 represents a substituted or unsubstituted C 6-30 aryl group, substituted or unsubstituted C 5-30 containing at least one hetero atom selected from the group consisting of N, O, and S; a heteroaryl group; A 1 represents a substituted or unsubstituted C 6-36 aryl group, substituted or unsubstituted C 5 containing at least one hetero atom selected from the group consisting of N, O, and S; -30heteroaryl ; X 1 and A 1 are the same or different, and at least one of them is substituted or unsubstituted, and contains at least one hetero atom selected from the group consisting of N, O, and S. 5-30heteroaryl ; and n represents an integer of 1 or 2, and when n represents 2, each of A 1 is the same or different.
於一具體實施態樣中,上述具式(I)結構之經喹啉取代之二苯基嘧啶化合物,係以式(I-1)結構或式(I-2)結構表示:
所述具式(I)結構之經喹啉取代之二苯基嘧啶化合物之A1為經取代或未經取代之C6-36芳基、經取代或未經取代之含有選自由N、O、及S所組成群組中之至少一雜原子之C5-30雜芳基,係由於該平面結構愈多,可有助於分子堆疊,增加其載子之傳輸效果,惟,其所選基團碳數不宜過多,避免形成不必要的結晶。 The A 1 of the quinoline-substituted diphenylpyrimidine compound having the structure of the formula (I) is a substituted or unsubstituted C 6-36 aryl group, and the substituted or unsubstituted one is selected from N, O. And the C 5-30 heteroaryl group of at least one hetero atom in the group consisting of S, because the planar structure is more, it can contribute to molecular stacking and increase the transport effect of the carrier, but it is selected The carbon number of the group should not be too much to avoid unnecessary crystallization.
所述具式(I)結構之經喹啉取代之二苯基嘧啶化合物 之X1為經取代或未經取代之C6-30芳基、經取代或未經取代之含有選自由N、O、及S所組成群組中之至少一雜原子之C5-30雜芳基,具有抑制分子結晶之作用。於一具體實施態樣中,X1為吡啶基、喹啉基或萘基。 The X 1 of the quinoline-substituted diphenylpyrimidine compound having the structure of the formula (I) is a substituted or unsubstituted C 6-30 aryl group, and the substituted or unsubstituted one is selected from N, O. And a C 5-30 heteroaryl group of at least one hetero atom in the group consisting of S, which has the effect of inhibiting molecular crystallization. In one embodiment, X 1 is pyridyl, quinolinyl or naphthyl.
於另一具體實施態樣中,上述具式(I)結構之經喹啉取代之二苯基嘧啶化合物,X1係選自下列所組成群組中之一者:
於一具體實施態樣中,A1係選自下列所組成群組中之一者:
於一具體實施態樣中,當n為1時,該式(I)化合物為式(I-3)或式(I-4)所示:
於一具體實施態樣中,當n為2時,該式(I)化合物為式(I-5)所示:
於另一具體實施態樣中,當n為2時,該A1為相同結構。 In another specific embodiment, when n is 2, the A 1 is the same structure.
文中,表達成「經取代或未經取代之」中的「經取代 之」表示在某個官能基中之氫原子係經另一個原子或基團(即取代基)置換。該等取代基各自獨立地選自由下列所組成之群組中之至少一者:氘、鹵素、C1-30烷基、C1-30烷氧基、C6-30芳基、C5-30雜芳基、經C6-30芳基取代之C5-30雜芳基、苯並咪唑基、C3-30環烷基、C5-7雜環烷基、三C1-30烷基矽烷基、三C1-30芳基矽烷基、二C1-30烷基C6-30芳基矽烷基、C1-30烷基二C6-30芳基矽烷基、C2-30烯基、C2-30炔基、氰基、二C1-30烷基胺基、二C6-30芳基硼基、二C1-30烷基硼基、C1-30烷基、C6-30芳基C1-30烷基、C1-30烷基C6-30芳基、羧基、硝基及羥基。 As used herein, "substituted" in "substituted or unsubstituted" means that a hydrogen atom in a functional group is replaced by another atom or group (ie, a substituent). The substituents are each independently selected from at least one of the group consisting of hydrazine, halogen, C 1-30 alkyl, C 1-30 alkoxy, C 6-30 aryl, C 5- 30 heteroaryl, C 5-30 heteroaryl substituted by C 6-30 aryl, benzimidazolyl, C 3-30 cycloalkyl, C 5-7 heterocycloalkyl, tri C 1-30 alkane Base alkyl, tri-C 1-30 aryl decyl, di C 1-30 alkyl C 6-30 aryl decyl, C 1-30 alkyl di C 6-30 aryl decyl, C 2-30 Alkenyl, C 2-30 alkynyl, cyano, di C 1-30 alkylamino, di C 6-30 aryl boron, di C 1-30 alkyl boron, C 1-30 alkyl, C 6-30 aryl C 1-30 alkyl, C 1-30 alkyl C 6-30 aryl, carboxyl, nitro and hydroxy.
文中,「芳基」表示芳基或(伸)芳基,該芳基係指衍生自芳香烴的單環系環或稠合環,及包括苯基、聯苯基、聯三苯基、萘基、聯萘基、苯基萘基、萘基苯基、茀基、苯基茀基、苯并茀基、二苯并茀基、菲基、苯基菲基、蒽基、茚基、聯伸三苯基、芘基、稠四苯基、苝基、蒯基、萘并萘基、丙二烯合茀基等。 As used herein, "aryl" means aryl or (extended) aryl, which means a monocyclic or fused ring derived from an aromatic hydrocarbon, and includes phenyl, biphenyl, triphenyl, naphthalene. , dinaphthyl, phenylnaphthyl, naphthylphenyl, anthracenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, phenylphenanyl, anthracenyl, fluorenyl, hydrazine Triphenyl, fluorenyl, fused tetraphenyl, anthracenyl, fluorenyl, naphtylnaphthyl, propadienyl fluorenyl and the like.
文中,「雜芳基」表示雜芳基或(伸)雜芳基,該雜芳基係指含有選自由N、O、及S所組成群組中之至少一個雜原子的環主鏈原子的芳基,可為單環系環,如呋喃基、噻吩基、吡咯基、咪唑基、吡唑基、噻唑基、噻二唑基、異噻唑基、異唑基、唑基、二唑基、三基、四基、三唑基、四唑基、呋呫基、吡啶基、吡基、嘧啶基、嗒基等,或為與至少一個苯環縮合的稠合環,如苯并呋喃基、苯并噻吩基、異苯并呋喃基、二苯并呋喃基、二苯并 噻吩基、苯并咪唑基、苯并噻唑基、苯并異噻唑基、苯并異唑基、喹啉基、異喹啉基、噌啉基、喹唑啉基、喹啉基、咔唑基、啡唑基、啡啶基、苯并二呃基、二氫吖啶基等。 Herein, "heteroaryl" means a heteroaryl group or a (hetero)heteroaryl group, and the heteroaryl group means a ring main chain atom containing at least one hetero atom selected from the group consisting of N, O, and S. An aryl group which may be a monocyclic ring such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, iso Azolyl, Azolyl, Diazolyl, three Base, four Base, triazolyl, tetrazolyl, furazolyl, pyridyl, pyridyl Base, pyrimidinyl, oxime a condensed ring condensed with at least one benzene ring, such as a benzofuranyl group, a benzothienyl group, an isobenzofuranyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzimidazolyl group, Benzothiazolyl, benzisothiazolyl, benzoid Azolyl, quinolyl, isoquinolyl, porphyrinyl, quinazolinyl, quin Orolinyl, carbazolyl, brown Azolyl, phenanthryl, benzodiazepine Mercapto, dihydroacridinyl and the like.
於一具體實施態樣中,前述具式(I)結構之經喹啉取代之二苯基嘧啶化合物之較佳實施例係選自於表1,但不限於此。 In a specific embodiment, the preferred embodiment of the quinoline-substituted diphenylpyrimidine compound having the structure of the formula (I) is selected from Table 1, but is not limited thereto.
於另一具體實施態樣中,上述具式(I)結構之經喹啉取代之二苯基嘧啶化合物,為化合物(1-10)或化合物(1-11)中的一者:
本發明之具式(I)結構之經喹啉取代之二苯基嘧啶化合物由於其玻璃轉化溫度介於98至165℃之間,尤以玻璃轉化溫度介於140至165℃之間為佳,可承受汽車內部長期的高溫,故適用於車用顯示器之有機電激發光元件。 The quinoline-substituted diphenylpyrimidine compound having the structure of the formula (I) of the present invention preferably has a glass transition temperature of from 98 to 165 ° C, particularly preferably a glass transition temperature of from 140 to 165 ° C. It can withstand the long-term high temperature inside the car, so it is suitable for organic electroluminescent components of automotive displays.
本發明復提供一種有機電激發光元件,包含:陰極;陽極;以及有機層,係介於該陰極與陽極之間,且該有機層包含本發明之具式(I)結構之經喹啉取代之二苯基嘧啶化合物。 The present invention provides an organic electroluminescent device comprising: a cathode; an anode; and an organic layer interposed between the cathode and the anode, and the organic layer comprises a quinoline substitution of the structure of the formula (I) of the present invention Diphenylpyrimidine compound.
本發明之有機電激發光元件之該有機層係可為電子傳輸層、電子注入層、發光層、電洞阻擋層或電子阻擋層,且除了該有機層外,該有機電激發光元件復可包括不同於該有機層的選自由電子傳輸層、電子注入層、發光層、電洞阻擋層及電子阻擋層所組成群組的至少一層,其中,該發光層復包含螢光或磷光摻質,以及分別對應螢光或磷光摻質之主體材料。 The organic layer of the organic electroluminescent device of the present invention may be an electron transport layer, an electron injection layer, a light emitting layer, a hole blocking layer or an electron blocking layer, and in addition to the organic layer, the organic electroluminescent device is reconfigurable And comprising at least one layer selected from the group consisting of an electron transport layer, an electron injection layer, a light emitting layer, a hole blocking layer and an electron blocking layer, wherein the light emitting layer further comprises a fluorescent or phosphorescent dopant, And a host material corresponding to the fluorescent or phosphorescent dopant, respectively.
於一具體實施態樣中,包含本發明之具式(I)結構之經喹啉取代之二苯基嘧啶化合物之有機層較佳為電子傳輸層,且其厚度係20奈米至30奈米;其中,該電子傳輸層可將具式(I)結構之經喹啉取代之二苯基嘧啶化合物做為單一材料,或將具式(I)結構之經喹啉取代之二苯基嘧啶化合物與電性傳導摻質結合使用。 In one embodiment, the organic layer comprising the quinoline-substituted diphenylpyrimidine compound of the formula (I) of the present invention is preferably an electron transport layer and has a thickness of from 20 nm to 30 nm. Wherein the electron transport layer can be a quinoline-substituted diphenylpyrimidine compound having the structure of the formula (I) as a single material, or a quinoline-substituted diphenylpyrimidine compound having the structure of the formula (I); Used in conjunction with electrically conductive dopants.
於另一具體實施態樣中,該電子傳輸層復包含N型電性傳導摻質,其中,該N型電性傳導摻質與本發明之具式(I)結構之經喹啉取代之二苯基嘧啶化合物產生螯合作用 (chelation),可使電子更容易地從陰極注入到電子傳輸層中,解決了現有技術中因金屬與電子傳輸主體材料的相容性較差而導致的相分離以及形成淬熄中心的問題,有效提高了電子傳輸層的電子傳輸效率。 In another embodiment, the electron transport layer further comprises an N-type electrically conductive dopant, wherein the N-type electrically conductive dopant is substituted with the quinoline substituted structure of the formula (I) of the present invention. Phenylpyrimidine compound produces chelation (chelation), which can make electrons more easily injected from the cathode into the electron transport layer, and solves the problem of phase separation and formation of quenching center caused by poor compatibility of metal and electron transport host materials in the prior art, and is effective. The electron transport efficiency of the electron transport layer is improved.
應用於電子傳輸層之N型電性傳導摻質係可為有機鹼金屬/鹼土金屬之硝酸鹽、碳酸鹽、磷酸鹽或喹啉酸鹽。具體而言,如碳酸鋰、喹啉鋰(lithium quinolate,Liq)、疊氮化鋰(lithium azide)、碳酸銣、硝酸銀、硝酸鋇、硝酸鎂、硝酸鋅、硝酸銫、碳酸銫、氟化銫、疊氮化銫等,其中,該N型電性傳導摻質尤以喹啉酸鋰為佳。 The N-type electrically conductive dopant system applied to the electron transport layer may be a nitrate, carbonate, phosphate or quinoline salt of an organic alkali metal/alkaline earth metal. Specifically, such as lithium carbonate, lithium quinolate (Liq), lithium azide, barium carbonate, silver nitrate, barium nitrate, magnesium nitrate, zinc nitrate, barium nitrate, barium carbonate, barium fluoride , azide, etc., wherein the N-type electrically conductive dopant is preferably lithium quinolate.
於一具體實施態樣中,以該電子傳輸層之重量計算,該N型電性傳導摻質的含量為5重量%至50重量%。 In one embodiment, the N-type electrically conductive dopant is present in an amount of from 5% by weight to 50% by weight based on the weight of the electron transporting layer.
本發明之有機電激發光元件之結構將配合圖式加以說明。 The structure of the organic electroluminescent device of the present invention will be described with reference to the drawings.
第1圖係本發明之有機電激發光元件之一具體實施例之剖面示意圖。有機電激發光元件100包含基板110、陽極120、電洞注入層130、電洞傳輸層140、發光層150、電子傳輸層160、電子注入層170及陰極180。有機電激發光元件100可經由依序沉積上述各層來製作。 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic cross-sectional view showing one embodiment of an organic electroluminescent device of the present invention. The organic electroluminescent device 100 includes a substrate 110, an anode 120, a hole injection layer 130, a hole transport layer 140, a light-emitting layer 150, an electron transport layer 160, an electron injection layer 170, and a cathode 180. The organic electroluminescent device 100 can be fabricated by sequentially depositing the above layers.
第2圖係本發明之有機電激發光元件之另一具體實施例之剖面示意圖。有機電激發光元件200包含基板210、陽極220、電洞注入層230、電洞傳輸層240、激子阻擋層245、發光層250、電子傳輸層260、電子注入層270及陰極280,與第1圖之差異在於該激子阻擋層245係設於電 洞傳輸層240與發光層250之間。 Fig. 2 is a schematic cross-sectional view showing another embodiment of the organic electroluminescent device of the present invention. The organic electroluminescent device 200 includes a substrate 210, an anode 220, a hole injection layer 230, a hole transport layer 240, an exciton blocking layer 245, a light emitting layer 250, an electron transport layer 260, an electron injection layer 270, and a cathode 280, and The difference between the figures is that the exciton blocking layer 245 is electrically connected. The hole transport layer 240 is between the light emitting layer 250.
第3圖係本發明之有機電激發光元件之又一具體實施例之剖面示意圖。有機電激發光元件300包含基板310、陽極320、電洞注入層330、電洞傳輸層340、發光層350、激子阻擋層355、電子傳輸層360、電子注入層370及陰極380,與第1圖之差異在於該激子阻擋層355係設於發光層350與電子傳輸層360之間。 Figure 3 is a schematic cross-sectional view showing still another embodiment of the organic electroluminescent device of the present invention. The organic electroluminescent device 300 includes a substrate 310, an anode 320, a hole injection layer 330, a hole transport layer 340, a light-emitting layer 350, an exciton blocking layer 355, an electron transport layer 360, an electron injection layer 370, and a cathode 380, and The difference in FIG. 1 is that the exciton blocking layer 355 is disposed between the light emitting layer 350 and the electron transport layer 360.
可依第1圖至第3圖所示元件之反置式結構(reverse structure)製造有機電激發光元件。於該等反置式結構可視需求增減一層或數層。 The organic electroluminescent device can be fabricated in accordance with the reverse structure of the elements shown in FIGS. 1 to 3. One or more layers are added or removed as needed for such inverted structures.
所述之電洞注入層、電洞傳輸層、激子阻擋層、電子阻擋層、電子注入層之材料可選擇習用材料,舉例來說,形成電子傳輸層之電子傳輸材料不同於發光層之材料,且其具有電洞傳輸性,從而促成電洞於電子傳輸層中遷移,且防止因發光層與電子傳輸層之解離能差所導致的載子累積。 The material of the hole injection layer, the hole transport layer, the exciton blocking layer, the electron blocking layer, and the electron injection layer may be selected from conventional materials. For example, the electron transporting material forming the electron transporting layer is different from the material of the light emitting layer. And it has hole transportability, thereby facilitating migration of holes in the electron transport layer, and preventing carrier accumulation due to dissociation energy difference between the light-emitting layer and the electron transport layer.
本發明之具式(I)結構之經喹啉取代之二苯基嘧啶化合物用於電子傳輸層,因具有高於2.2eV之三重態能量(ET)及良好的載子遷移率,有助於提升激子於發光層內鬆弛而發射光。 The quinoline-substituted diphenylpyrimidine compound of the formula (I) of the present invention is used for an electron transport layer, and has a triplet energy (E T ) higher than 2.2 eV and good carrier mobility, which is helpful. The exciter is lifted in the luminescent layer to emit light.
此外,第20170005275A1號美國專利所例示p型摻雜之電洞傳輸層係以HT-D2摻雜於HT3中,其全部內容為本發明所引用,且該專利亦使用Lithium quinolate(Liq)作為n型摻雜材料來摻雜在電子傳輸材料(ET3)中,其全部內容 為本發明所引用。如第5703436及5707745號美國專利所例示陰極之全部內容為本發明所引用,該陰極具有金屬薄層,如:鎂/銀(Mg:Ag),及以濺鍍沉積覆蓋金屬薄層之透明導電層(ITO Layer)。第6097147及20030230980號美國專利所揭示各阻擋層之應用及原理,其全部內容為本發明所引用。第20040174116號美國專利所例示之注入層及同案所說明之保護層,其全部內容為本發明所引用。 In addition, U.S. Patent No. 20170005275A1 exemplifies that a p-type doped hole transport layer is doped with HT-D2 in HT3, the entire contents of which are cited in the present application, and the patent also uses Lithium quinolate (Liq) as n Type doping material to be doped in electron transport material (ET3), its full content It is cited for the present invention. The entire contents of the cathodes as exemplified in U.S. Patent Nos. 5, 573, 436 and 5, 707, 745, which are incorporated herein by reference in their entirety, the disclosures of ITO Layer. The application and principles of the various barrier layers disclosed in U.S. Patent Nos. 6,097,147 and 2,030, 030, 980 are incorporated herein by reference. The injection layer exemplified in U.S. Patent No. 2,040,174,116 and the protective layer described in the same application are hereby incorporated by reference.
未特別說明之結構及材料亦可應用於本發明,如第5247190號美國專利所揭示包括聚合物材料(PLEDs)之有機電激發光元件,其全部內容為本發明所引用。再者,具有單一有機層之有機電激發光元件或如第5707745號美國專利所揭示堆疊形成之有機電激發光元件,其全部內容為本發明所引用。 Structures and materials that are not specifically described are also applicable to the present invention. Organic electroluminescent elements comprising polymeric materials (PLEDs) are disclosed in U.S. Patent No. 5,247,190, the entire disclosure of which is incorporated herein by reference. Further, an organic electroluminescent device having a single organic layer or an organic electroluminescent device formed by stacking as disclosed in U.S. Patent No. 5,707,745, the entire disclosure of which is incorporated herein.
除有特別限定,不同實施例中之任何層可使用任何適當方法來沉積形成。以有機層而言,較佳之方法包含如第6013982及6087196號美國專利所揭示之熱蒸鍍法及噴印法,其全部內容為本發明所引用;第6337102號美國專利所揭示有機氣相沉積法(organic vapor phase deposition,OVPD),其全部內容為本發明所引用;第10/233470號美國專利所揭示有機氣相噴印沉積法(deposition by organic vapor jet printing,OVJP),其全部內容為本發明所引用。其他適當方法包含旋轉塗佈及以溶液為基礎之製程。以溶液為基礎之製程較佳是在氮氣或惰性氣體環境中進行。對於其他之層而言,較佳之方法包含熱蒸鍍法。較佳的圖案 化方法包含如第6294398及6468819號美國專利所揭示通過遮罩沉積再冷焊之製程,及整合噴印或有機氣相噴印沉積與圖案化之製程,其全部內容為本發明所引用。當然亦可使用其他方法。用於沉積之材料可予調整以對應其所特用之沉積方法。 Unless otherwise specified, any of the various embodiments may be deposited using any suitable method. In the case of the organic layer, the preferred method comprises the thermal evaporation method and the printing method as disclosed in U.S. Patent Nos. 6,013,982 and 6,087,196, the entire disclosure of which is incorporated herein by reference. Organic vapor phase deposition (OVPD), the entire disclosure of which is incorporated herein by reference. U.S. Patent No. 10/233,470, the disclosure of which is incorporated herein by reference. The invention is cited. Other suitable methods include spin coating and solution based processes. The solution based process is preferably carried out in a nitrogen or inert gas atmosphere. For other layers, the preferred method involves thermal evaporation. Preferred pattern The process includes a process for re-cold deposition by mask deposition as disclosed in U.S. Patent Nos. 6,294,398 and 6,468,819, and a process for integrated printing or organic vapor deposition deposition and patterning, the entire contents of which are incorporated herein by reference. Of course, other methods can also be used. The material used for deposition can be adjusted to correspond to the deposition method it is used for.
本發明具式(I)結構之經喹啉取代之二苯基嘧啶化合物係能以真空沉積或濕式塗佈法製成應用於有機電激發光元件之非晶性薄膜。當該化合物使用於任一之上述有機層,其展現出較長使用壽命及良好的熱穩定性。 The quinoline-substituted diphenylpyrimidine compound having the structure of the formula (I) of the present invention can be formed into an amorphous thin film applied to an organic electroluminescent device by vacuum deposition or wet coating. When the compound is used in any of the above organic layers, it exhibits a long service life and good thermal stability.
本發明之有機電激發光元件可應用於單一元件,其結構為陣列配置或陣列X-Y座標中設有陰陽兩極之元件。相較於習知元件,本發明能顯著提升有機電激發光元件之使用壽命及驅動穩定性。此外,與發光層中之磷光摻質相結合,本發明之有機電激發光元件應用於全彩或多彩顯示面板能實現較佳性能且可發射白光。 The organic electroluminescent device of the present invention can be applied to a single component, and its structure is an array configuration or an element having an anode and a cathode in the X-Y coordinate of the array. Compared with the conventional components, the present invention can significantly improve the service life and driving stability of the organic electroluminescent device. In addition, in combination with the phosphorescent dopant in the light-emitting layer, the organic electroluminescent device of the present invention can be applied to a full-color or colorful display panel to achieve better performance and emit white light.
以下藉由實施例詳細說明本發明之諸多性質及功效。該等詳述實施例僅用於說明本發明之性質,本發明不限於特定實施例所例示者。 The nature and efficacy of the present invention are described in detail below by way of examples. The detailed description is merely illustrative of the nature of the invention, and the invention is not limited to the specific embodiments.
合成例1:化合物1-1之合成Synthesis Example 1: Synthesis of Compound 1-1
將4-溴苯乙酮(4-Bromoacetophenone)(10g, 50.23mmole)與喹啉-8-硼酸(quinolin-8-ylboronic acid)(9.12g,52.75mmole)置於反應槽內,加入120毫升的甲苯,並且將碳酸鉀(18.05g,130.6mmole)溶於70毫升的去離子水後亦加入反應槽,同時加入四(三苯基膦)鈀(Pd(PPh3)4)(1.74g,1.507mmole)及30毫升的乙醇,並開啟加熱及攪拌,加熱直至80℃並反應隔夜。待反應完成後加入300毫升的去離子水,經攪拌30分鐘後停止攪拌並靜置使其分層,去除水層後,用矽膠層析法純化,濃縮至濃稠態後再加入300毫升的己烷析出,有機層合併過濾固體,得淡黃色固體A(約8克)。 4-Bromoacetophenone (10 g, 50.23 mmole) and quinolin-8-ylboronic acid (9.12 g, 52.75 mmole) were placed in a reaction tank, and 120 ml was added. Toluene, and potassium carbonate (18.05 g, 130.6 mmole) was dissolved in 70 ml of deionized water and added to the reaction tank while adding tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (1.74 g, 1.507). Mmmol) and 30 ml of ethanol, and heated and stirred, heated to 80 ° C and reacted overnight. After the reaction was completed, 300 ml of deionized water was added. After stirring for 30 minutes, the stirring was stopped and allowed to stand for stratification. After removing the aqueous layer, it was purified by silica gel chromatography, concentrated to a thick state, and then 300 ml was added. The hexane was precipitated and the organic layer was combined and filtered to give a pale yellow solid A (~8 g).
將該淡黃色固體A(10g,40.737mmole)與4-溴苯甲醛(4-bromobenzaldehyde)(8.23g,44.48mmole)置於反應槽,充分除水後,加入230毫升的乙醇,開啟攪拌,並添加甲醇鈉(0.655g,12.31mmole),於室溫攪拌16小時。其後,添加3-吡啶偕胺肟鹽酸鹽(3-Amidinopyridinium chloride)(6.7g,44.34mmole)與氫氧化鈉(3.22g,80.61mmole),並追加入30毫升的甲苯,打開加熱裝置,加熱直至75℃並反應隔夜。待反應完後,過濾取固體,再以250毫升的甲苯 加熱攪拌並過濾固體,得乳白色固體B(約5.5克)。 The pale yellow solid A (10 g, 40.737 mmole) and 4-bromobenzaldehyde (8.23 g, 44.48 mmole) were placed in a reaction tank, and after thoroughly removing water, 230 ml of ethanol was added to start stirring. Sodium methoxide (0.655 g, 12.31 mmole) was added and stirred at room temperature for 16 h. Thereafter, 3-Amidinopyridinium chloride (6.7 g, 44.34 mmole) and sodium hydroxide (3.22 g, 80.61 mmole) were added, and 30 ml of toluene was added thereto, and the heating device was turned on. Heat to 75 ° C and react overnight. After the reaction is completed, the solid is collected by filtration, and then 250 ml of toluene is added. The mixture was heated to stir and the solid was filtered to give a white solid B (about 5.5 g).
將該乳白色固體B(10g,19.40mmole)與4-二苯并呋喃硼酸(dibenzo[b,d]furan-4-ylboronic acid)(4.936g,23.38mmole)置於反應槽內,加入120毫升的甲苯。將碳酸鉀(9.384g,67.9mmole)溶於70毫升的去離子水後加入反應槽,加入四(三苯基膦)鈀(Pd(PPh3)4)(1.12g,0.97mmole)及30毫升的乙醇開啟加熱及攪拌,加熱直至80℃並反應隔夜。待反應完後,加入300毫升的去離子水,攪拌30分鐘後停止攪拌並靜置使其分層,進行過濾,使用索氏萃取器收到粗品,使用索氏萃取器加入矽膠進行層析法純化,濃縮至濃稠態加入300毫升的己烷加強析出,有機層合併過濾固體,得乳白色固體化合物1-1(約5.1克)。 The milky white solid B (10 g, 19.40 mmole) and 4-dibenzofuran boronic acid (dibenzo[b,d]furan-4-ylboronic acid) (4.936 g, 23.38 mmole) were placed in a reaction tank, and 120 ml was added. Toluene. Potassium carbonate (9.384 g, 67.9 mmole) was dissolved in 70 ml of deionized water and added to the reaction tank, and tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (1.12 g, 0.97 mmole) and 30 ml were added. The ethanol was heated and stirred, heated to 80 ° C and reacted overnight. After the reaction was completed, 300 ml of deionized water was added, stirred for 30 minutes, the stirring was stopped, and the mixture was allowed to stand for stratification, filtered, and the crude product was received using a Soxhlet extractor, and the tannin extract was used for chromatography. Purification, concentration to a thick state, EtOAc (3 mL), EtOAc (EtOAc)
化合物1-1 1HNMR:1H NMR(CDCl3,400MHz),δ 10-9.9(S,1H);9.02-8.99(m,2H);8.85-8.82(d,1H);8.45-8.26(m,5H);8.2-7.45(m,17H). Compound 1-1 1 H NMR: 1 H NMR (CDCl 3 , 400 MHz), δ 10-9.9 (S, 1H); 9.02-8.99 (m, 2H); 8.85-8.82 (d, 1H); 8.45-8.26 (m) , 5H); 8.2-7.45 (m, 17H).
合成例2:化合物1-2之合成Synthesis Example 2: Synthesis of Compound 1-2
將反應物A(10g,40.737mmole)與3-溴苯甲醛(3-bromobenzaldehyde)(8.23g,44.48mmole)置於反應槽,充分除水後,加入230毫升的乙醇,開啟攪拌,並添加甲醇鈉(0.655g,12.31mmole),於室溫攪拌16小時。其後,添加3-吡啶偕胺肟鹽酸鹽(3-Amidinopyridinium chloride)(6.7g,44.34mmole)與氫氧化鈉(3.22g,80.61mmole),並追加入30毫升的甲苯,打開加熱裝置,加熱直至75℃並反應隔夜。待反應完後,過濾取固體,再以250毫升的甲苯加熱攪拌並過濾固體,得乳白色固體C(約5克)。 The reactant A (10 g, 40.737 mmole) and 3-bromobenzaldehyde (8.23 g, 44.48 mmole) were placed in a reaction tank, and after thoroughly removing water, 230 ml of ethanol was added, stirring was started, and methanol was added. Sodium (0.655 g, 12.31 mmole) was stirred at room temperature for 16 h. Thereafter, 3-Amidinopyridinium chloride (6.7 g, 44.34 mmole) and sodium hydroxide (3.22 g, 80.61 mmole) were added, and 30 ml of toluene was added thereto, and the heating device was turned on. Heat to 75 ° C and react overnight. After completion of the reaction, the solid was filtered, and then stirred and stirred with 250 ml of toluene, and the solid was filtered to give a white solid C (about 5 g).
將該乳白色固體C(10g,19.40mmole)與4-二苯并呋喃硼酸(dibenzo[b,d]furan-4-ylboronic acid)(4.936g,23.38mmole)置於反應槽內,加入120毫升的甲苯。將碳酸鉀(9.384g,67.9mmole)溶於70毫升的去離子水後加入反應槽,加入四(三苯基膦)鈀(Pd(PPh3)4)(1.12g,0.97mmole) 及30毫升的乙醇開啟加熱及攪拌,加熱直至80℃反應並隔夜。待反應完後,加入300毫升的去離子水,攪拌30分鐘後,停止攪拌靜置使其分層,進行過濾,收到粗品,使用索氏萃取器加入矽膠進行層析法純化,濃縮至濃稠態加入300毫升的己烷加強析出,有機層合併過濾固體,得乳白色固體化合物1-2(約5.5克)。 The milky white solid C (10 g, 19.40 mmole) and 4-dibenzofuran boronic acid (dibenzo[b,d]furan-4-ylboronic acid) (4.936 g, 23.38 mmole) were placed in a reaction tank, and 120 ml was added. Toluene. Potassium carbonate (9.384 g, 67.9 mmole) was dissolved in 70 ml of deionized water and added to the reaction tank, and tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (1.12 g, 0.97 mmole) and 30 ml were added. The ethanol was heated and stirred, heated to 80 ° C and allowed to react overnight. After the reaction was completed, 300 ml of deionized water was added, and after stirring for 30 minutes, the stirring was stopped, the mixture was allowed to stand, and the mixture was filtered. The crude product was obtained, and the mixture was purified by chromatography using a Soxhlet extractor, and concentrated to a thick concentration. The solid phase was added to a solution of 300 ml of hexane to enhance precipitation, and the organic layer was combined and filtered to give a white solid compound 1-2 (about 5.5 g).
化合物1-2 1HNMR:1H NMR(CDCl3,400MHz),δ 10-9.92(S,1H);9.02-8.99(m,2H);8.85-8.82(S,1H);8.85-8.7(d,1H);8.44-8.41(d,2H);8.39-8.36(d,1H);8.35-7.47(m,18H). Compound 1-2 1 H NMR: 1 H NMR (CDCl 3 , 400 MHz), δ 10-9.92 (S, 1H); 9.02-8.99 (m, 2H); 8.85-8.82 (S, 1H); 8.85-8.7 (d) , 1H); 8.44 - 8.41 (d, 2H); 8.39-8.36 (d, 1H); 8.35-7.47 (m, 18H).
合成例3:化合物1-3之合成Synthesis Example 3: Synthesis of Compound 1-3
將反應物C(10g,19.4mmole)與4-二苯并噻吩硼酸(dibenzo[b,d]thiophen-4-ylboronic acid)(5.31g,23.28mmole)置於反應槽內,加入120毫升的甲苯。將碳酸鉀(9.38g,67.9mmole)溶於70毫升的去離子水後加入反應槽,加入四(三苯基膦)鈀(Pd(PPh3)4)(1.12g,0.97mmole)及30毫升的乙醇開啟加熱及攪拌,加熱直至80℃並反應隔夜。待反應完後,加入300毫升的去離子水,攪拌30分鐘後停 止攪拌靜置使其分層,去除水層後,用矽膠層析法純化,濃縮至濃稠態加入300毫升的己烷析出,有機層合併過濾固體,得乳白色固體化合物1-3(約8克)。 The reactant C (10 g, 19.4 mmole) and dibenzo[b,d]thiophen-4-ylboronic acid (5.31 g, 23.28 mmole) were placed in a reaction tank, and 120 ml of toluene was added. . Potassium carbonate (9.38 g, 67.9 mmole) was dissolved in 70 ml of deionized water and added to the reaction tank, and tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (1.12 g, 0.97 mmole) and 30 ml were added. The ethanol was heated and stirred, heated to 80 ° C and reacted overnight. After the reaction was completed, 300 ml of deionized water was added, and after stirring for 30 minutes, the stirring was stopped and allowed to stand, and the layers were separated. After removing the aqueous layer, it was purified by silica gel chromatography, and concentrated to a thick state to be added with 300 ml of hexane. The organic layer was combined and filtered to give a white solid solid compound 1-3 (~8 g).
化合物1-3 1HNMR:1H NMR(CDCl3,400MHz),δ 9.96-9.94(S,1H);9.01-8.99(m,2H):8.76-8.75(d,1H);8.72-8.71(S,1H);8.45-8.38(m,3H);8.25-8.23(m,4H);7.95-7.44(m,14H). Compound 1-3 1 H NMR: 1 H NMR (CDCl 3 , 400 MHz), δ 9.96-9.94 (S, 1H); 9.01-8.99 (m, 2H): 8.76-8.75 (d, 1H); 8.72-8.71 , 1H); 8.45-8.38 (m, 3H); 8.25-8.23 (m, 4H); 7.95-7.44 (m, 14H).
合成例4:化合物1-5之合成Synthesis Example 4: Synthesis of Compounds 1-5
將反應物C(10g,19.4mmole)與4-(1-苯基-1H-苯并咪唑-2-基)苯基硼酸(4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)boronic acid)(7.31g,23.28mmole)置於反應槽,加入120毫升的甲苯。將碳酸鉀(9.38g,67.9mmole)溶於70毫升的去離子水後加入反應槽,加入四(三苯基膦)鈀(Pd(PPh3)4)(1.12g,0.97mmole)及30毫升的乙醇開啟加熱及攪拌,加熱直至80℃並反應隔夜。待反應完後,加入300毫升的去離子水,攪拌30分鐘後,停止攪拌靜置使其分層,去除水層後,用矽膠層析法純化,濃縮至濃稠態加入300 毫升的己烷析出,有機層合併過濾固體,得到淡綠色固體化合物1-5(約7.5克)。 Reaction C (10 g, 19.4 mmole) with 4-(1-phenyl-1H-benzimidazol-2-yl)phenylboronic acid (4-(1-phenyl-1H-benzo[d]imidazol-2- Yl)phenyl)boronic acid) (7.31 g, 23.28 mmole) was placed in a reaction tank, and 120 ml of toluene was added. Potassium carbonate (9.38 g, 67.9 mmole) was dissolved in 70 ml of deionized water and added to the reaction tank, and tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (1.12 g, 0.97 mmole) and 30 ml were added. The ethanol was heated and stirred, heated to 80 ° C and reacted overnight. After the reaction was completed, 300 ml of deionized water was added, and after stirring for 30 minutes, the stirring was stopped and allowed to stand for stratification. After removing the aqueous layer, it was purified by silica gel chromatography and concentrated to a thick state to add 300 ml of hexane. The organic layer was combined and filtered to give a pale green solid compound 1-5 (about 7.5 g).
化合物1-5 1HNMR:1H NMR(CDCl3,400MHz),δ 9.94-9.92(S,1H);8.99-8.98(m,3H);8.76-8.76(m,1H);8.45-8.44(S,2H);8.44-8.42(d,3H);8.27-8.25(t,3H);8.19-8.17(S,2H);7.93-7.3(m,17H). Compound 1-5 1 H NMR: 1 H NMR (CDCl 3 , 400 MHz), δ 9.94-9.92 (S, 1H); 8.99-8.98 (m, 3H); 8.76-8.76 (m, 1H); 8.45-8.44 (S , 2H); 8.44-8.42 (d, 3H); 8.27-8.25 (t, 3H); 8.19-8.17 (S, 2H); 7.93-7.3 (m, 17H).
合成例5:化合物1-6之合成Synthesis Example 5: Synthesis of Compounds 1-6
將反應物C(10g,19.40mmole)與3-(3-吡啶基)苯硼酸((3-(pyridin-3-yl)phenyl)boronic acid)(4.633g,23.28mmole)置於反應槽內,加入120毫升的甲苯。將碳酸鉀(9.384g,67.9mmole)溶於70毫升的去離子水後加入反應槽,加入四(三苯基膦)鈀(Pd(PPh3)4)(1.12g,0.97mmole)及30毫升的乙醇開啟加熱及攪拌,加熱直至80℃並反應隔夜。待反應完後,加入300毫升的去離子水,攪拌30分鐘後停止攪拌靜置使其分層,進行過濾,收到粗品,使用索氏萃取器加入矽膠進行層析法純化,濃縮至濃稠態加入300毫升的己烷加強析出,有機層合併過濾固體,得乳白色固體化合物 1-6(約4.3克)。 The reactant C (10 g, 19.40 mmole) and 3-(pyridin-3-yl)phenylboronic acid (4.633 g, 23.28 mmole) were placed in a reaction tank. Add 120 ml of toluene. Potassium carbonate (9.384 g, 67.9 mmole) was dissolved in 70 ml of deionized water and added to the reaction tank, and tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (1.12 g, 0.97 mmole) and 30 ml were added. The ethanol was heated and stirred, heated to 80 ° C and reacted overnight. After the reaction was completed, 300 ml of deionized water was added, and after stirring for 30 minutes, the stirring was stopped, the mixture was allowed to stand, and the mixture was filtered. The crude product was obtained, and the mixture was purified by chromatography using a Soxhlet extractor and concentrated to a thick consistency. The precipitate was added to a mixture of 300 ml of hexane, and the organic layer was combined and filtered to give a white solid solid compound 1-6 (about 4.3 g).
化合物1-6 1HNMR:1H NMR(CDCl3,400MHz),δ 9.9-9.8(S,1H);8.99-8.95(m,3H);8.79-8.75(t,1H);8.64-8.63(d,1H);8.54-8.51(S,1H);8.45-8.43(d,3H);8.26-8.25(d,2H);8.25-8.21(d,1H);8.20-7.99(S,1H);7.99-7.40(m,13H). Compound 1-6 1 H NMR: 1 H NMR (CDCl 3 , 400 MHz), δ 9.9-9.8 (S, 1H); 8.99-8.95 (m, 3H); 8.79 - 8.75 (t, 1H); 8.64 - 8.63 (d , 1H); 8.54-8.51 (S, 1H); 8.45-8.43 (d, 3H); 8.26-8.25 (d, 2H); 8.25-8.21 (d, 1H); 8.20-7.99 (S, 1H); -7.40 (m, 13H).
合成例6:化合物1-7之合成Synthesis Example 6: Synthesis of Compound 1-7
將化合物A(10g,40.737mmole)與3,5-二溴苯甲醛(3,5-dibromobenzaldehyde)(11.74g,44.48mmole)置於反應槽,充分除水後加入230毫升的乙醇,開啟攪拌,並添加甲醇鈉(0.655g,12.31mmole),於室溫攪拌16小時。其後,添加3-吡啶偕胺肟鹽(3-Amidinopyridinium chloride)(6.7g,44.34mmole)與氫氧化鈉(3.22g,80.61mmole),並追加入30毫升的甲苯,打開加熱裝置,加熱直至75℃並反應隔夜。待反應完後,過濾取固體,再以250毫升的甲苯加熱攪拌並過濾固體,得乳白色固體化合物D(約6.3克)。 Compound A (10 g, 40.737 mmole) and 3,5-dibromobenzaldehyde (11.74 g, 44.48 mmole) were placed in a reaction tank, and after thoroughly removing water, 230 ml of ethanol was added thereto, and stirring was started. Sodium methoxide (0.655 g, 12.31 mmole) was added and stirred at room temperature for 16 h. Thereafter, 3-Amidinopyridinium chloride (6.7 g, 44.34 mmole) and sodium hydroxide (3.22 g, 80.61 mmole) were added, and 30 ml of toluene was added thereto, and the heating device was turned on and heated until 75 ° C and react overnight. After completion of the reaction, the solid was filtered, and then stirred and stirred with 250 ml of toluene, and the solid was filtered to give a white solid compound D (about 6.3 g).
將化合物D(10g,16.83mmole)與1-萘基硼酸(1-Naphthalenylboroni甲苯/乙醇/水,回流,42.07mmole)置於反應槽,加入120毫升的甲苯。將碳酸鉀(18.768g,135.8mmole)溶於70毫升的去離子水後加入反應槽,加入四(三苯基膦)鈀(Pd(PPh3)4)(2.24g,1.94mmole)及30毫升的乙醇開啟加熱及攪拌,加熱直至80℃反應並隔夜。待反應完後,加入300毫升的去離子水,攪拌30分鐘後,停止攪拌靜置使其分層,進行過濾,收到粗品,使用索氏萃取器加入矽膠進行層析法純化,濃縮至濃稠態加入300毫升的己烷加強析出,有機層合併過濾固體,得乳白色固體化合物1-7(約6.5克)。1H NMR(CDCl3,400MHz),δ 9.916(d,1H),8.95-8.98(m,2H),8.73(dd,1H),8.52(d,2H),8.42(d,2H),8.23-8.25(m,2H),8.13(d,2H),7.98(m,4H),7.88(m,4H),7.81(d,1H),7.61-7.67(m,5H),7.51-7.56(m,4H),7.41-7.50(m,2H). Compound D (10 g, 16.83 mmole) and 1-naphthylboronic acid (1-Naphthalenylboroni toluene/ethanol/water, reflux , 42.07 mmole) were placed in a reaction vessel, and 120 ml of toluene was added. Potassium carbonate (18.768 g, 135.8 mmole) was dissolved in 70 ml of deionized water and added to the reaction tank, and tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (2.24 g, 1.94 mmole) and 30 ml were added. The ethanol was heated and stirred, heated to 80 ° C and allowed to react overnight. After the reaction was completed, 300 ml of deionized water was added, and after stirring for 30 minutes, the stirring was stopped, the mixture was allowed to stand, and the mixture was filtered. The crude product was obtained, and the mixture was purified by chromatography using a Soxhlet extractor, and concentrated to a thick concentration. The solid phase was added to a solution of 300 ml of hexane to enhance precipitation, and the organic layer was combined and filtered to give a white solid solid compound 1-7 (about 6.5 g). 1 H NMR (CDCl 3, 400MHz ), δ 9.916 (d, 1H), 8.95-8.98 (m, 2H), 8.73 (dd, 1H), 8.52 (d, 2H), 8.42 (d, 2H), 8.23- 8.25(m,2H), 8.13(d,2H), 7.98(m,4H),7.88(m,4H),7.81(d,1H), 7.61-7.67(m,5H),7.51-7.56(m, 4H), 7.41-7.50 (m, 2H).
合成例7:化合物1-8之合成Synthesis Example 7: Synthesis of Compound 1-8
將反應物C(10g,19.40mmole)與喹啉-8-硼酸(quinolin-8-ylboronic acid)(4.027g,23.28mmole)置於反應槽內,加入120毫升的甲苯。將碳酸鉀(9.384g,67.9mmole)溶於70毫升的去離子水後加入反應槽,加入四(三苯基膦)鈀(Pd(PPh3)4)(1.12g,0.97mmole)及30毫升的乙醇開啟加熱及攪拌,加熱直至80℃並反應隔夜。待反應完後,加入300毫升的去離子水,攪拌30分鐘後停止攪拌並靜置使其分層,進行過濾收到粗品,使用索氏萃取器加入矽膠進行層析法純化,濃縮至濃稠態加入300毫升的己烷加強析出,有機層合併過濾固體,得乳白色固體化合物1-8(約5.5克)。 Reaction C (10 g, 19.40 mmole) and quinolin-8-ylboronic acid (4.027 g, 23.28 mmole) were placed in a reaction vessel, and 120 ml of toluene was added. Potassium carbonate (9.384 g, 67.9 mmole) was dissolved in 70 ml of deionized water and added to the reaction tank, and tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (1.12 g, 0.97 mmole) and 30 ml were added. The ethanol was heated and stirred, heated to 80 ° C and reacted overnight. After the reaction was completed, 300 ml of deionized water was added, and after stirring for 30 minutes, the stirring was stopped and allowed to stand for stratification, and the crude product was obtained by filtration, and the mixture was purified by chromatography using a Soxhlet extractor, and concentrated to a thick layer. The precipitate was added to a mixture of 300 ml of hexane, and the organic layer was combined and filtered to give a white solid solid compound 1-8 (about 5.5 g).
化合物1-8 1HNMR:1H NMR(CDCl3,400MHz),δ9.95-9.9(S,1H);8.99-8.98(m,3H);8.75-8.74(d,1H);8.62-8.62(S,1H);8.43-8.42(d,2H);8.41-8.37(d,1H);8.27-8.27(m,3H);7.92-7.4(m,13H). Compound 1-8 1 H NMR: 1 H NMR (CDCl 3 , 400 MHz), δ 9.95-9.9 (S, 1H); 8.99-8.98 (m, 3H); 8.75-8.74 (d, 1H); 8.62. S, 1H); 8.43-8.42 (d, 2H); 8.41-8.37 (d, 1H); 8.27-8.27 (m, 3H); 7.92-7.4 (m, 13H).
合成例8:化合物1-10之合成Synthesis Example 8: Synthesis of Compound 1-10
將反應物C(10g,19.4mmole)與(10-苯基蒽-9基)-硼酸((10-phenylanthracen-9-yl)boronic acid)(6.36g,21.32mmole)置於反應槽,加入120毫升的甲苯。將碳酸鉀(9.38g,67.9mmole)溶於70毫升的去離子水後加入反應槽,加入四(三苯基膦)鈀(Pd(PPh3)4)(0.67g,0.582mmole)及30毫升的乙醇開啟加熱及攪拌,加熱直至80℃並隔夜反應。待反應完後,加入300毫升的去離子水,攪拌30分鐘後停止攪拌靜置使其分層,去除水層後,用矽膠層析法純化,濃縮至濃稠態加入300毫升的己烷析出,有機層合併過濾固體,得淡黃色固體化合物1-10(約3.2克)。 The reactant C (10 g, 19.4 mmole) and (10-phenylanthracen-9-yl) boronic acid (6.36 g, 21.32 mmole) were placed in a reaction tank, and 120 was added. ML of toluene. Potassium carbonate (9.38 g, 67.9 mmole) was dissolved in 70 ml of deionized water and added to the reaction tank, and tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (0.67 g, 0.582 mmole) and 30 ml were added. The ethanol was heated and stirred, heated to 80 ° C and reacted overnight. After the reaction was completed, 300 ml of deionized water was added, and after stirring for 30 minutes, the stirring was stopped and allowed to stand, and the layers were separated. After removing the aqueous layer, it was purified by silica gel chromatography, and concentrated to a thick state to be added with 300 ml of hexane. The organic layer was combined and filtered to give a pale yellow solid compound 1-10 (~ 3.2 g).
化合物1-10 1HNMR:1H NMR(CDCl3,400MHz),δ9.95-9.93(S,1H);8.97-8.96(m,2H);8.74-8.72(m,1H);8.58-8.56(d,1H);8.56-8.54(m,3H);8.45-8.43(m,2H);7.93-7.66(m,22H). Compound 1-10 1 H NMR: 1 H NMR (CDCl 3 , 400 MHz), δ 9.95-9.93 (S, 1H); 8.97-8.96 (m, 2H); 8.74 - 8.72 (m, 1H); 8.58-8.56 ( d, 1H); 8.56-8.54 (m, 3H); 8.45-8.43 (m, 2H); 7.93-7.66 (m, 22H).
合成例9:化合物1-11之合成Synthesis Example 9: Synthesis of Compound 1-11
將反應物C與(10-[1,1'-聯苯]-4-基-9-蒽基)-硼酸(10-([1,1'-biphenyl]-4-yl)anthracen-9-yl)boronic acid(10.89g,29.1mmole)置於反應槽,加入120毫升的甲苯。將碳酸鉀(9.38g,67.9mmole)溶於70毫升的去離子水後加入反應槽,加入四(三苯基膦)鈀(Pd(PPh3)4)(0.56g,0.485mmole)及30毫升的乙醇開啟加熱及攪拌,加熱直至80℃。待反應完後,加入300毫升的去離子水,攪拌30分鐘後停止攪拌靜置使其分層,去除水層後,用矽膠層析法純化,濃縮至濃稠態加入300毫升的己烷析出,有機層合併過濾固體,得淡黃色固體化合物1-11(約4.4克)。 Reactant C with (10-[1,1'-biphenyl]-4-yl-9-mercapto)-boronic acid (10-([1,1'-biphenyl]-4-yl)anthracen-9- Yl) Boronic acid (10.89 g, 29.1 mmole) was placed in a reaction tank, and 120 ml of toluene was added. Potassium carbonate (9.38 g, 67.9 mmole) was dissolved in 70 ml of deionized water and added to the reaction tank, and tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (0.56 g, 0.485 mmole) and 30 ml were added. The ethanol was heated and stirred and heated to 80 °C. After the reaction was completed, 300 ml of deionized water was added, and after stirring for 30 minutes, the stirring was stopped and allowed to stand, and the layers were separated. After removing the aqueous layer, it was purified by silica gel chromatography, and concentrated to a thick state to be added with 300 ml of hexane. The organic layer was combined and filtered to give a pale yellow solid compound 1-11 (~ 4.4 g).
化合物1-11 1HNMR:1H NMR(CDCl3,400MHz),δ9.95-9.92(S,1H);8.95-8.93(m,2H);8.7-8.6(m,1H);8.58-8.56(d,1H);8.56-8.54(m,3H);8.420-8.402(m,2H);7.904-7.26(m,26H). Compound 1-11 1 H NMR: 1 H NMR (CDCl 3 , 400 MHz), δ 9.95-9.92 (S, 1H); 8.95-8.93 (m, 2H); 8.7-8.6 (m, 1H); 8.58-8.56 ( d, 1H); 8.56-8.54 (m, 3H); 8.420-8.402 (m, 2H); 7.094-7.26 (m, 26H).
合成例10:化合物1-15之合成Synthesis Example 10: Synthesis of Compound 1-15
將反應物C(10g,19.4mmole)與9,9'-螺二芴-2-基硼酸(9,9'-spirobi[fluoren]-2-ylboronic acid)(8.386g,23.2mmole)置於反應槽,加入120毫升的甲苯。將碳酸鉀(9.38g,67.9mmole)溶於70毫升的去離子水後加入反應槽,加入四(三苯基膦)鈀(Pd(PPh3)4)(0.672g,0.582mmole)及30毫升的乙醇開啟加熱及攪拌,加熱直至80℃並隔夜反應。待反應完後,加入300毫升的去離子水,攪拌30分鐘後停止攪拌靜置使其分層,去除水層後,用矽膠層析法純化,濃縮至濃稠態加入300毫升的己烷析出,有機層合併過濾固體,得乳白色固體化合物1-15(約7.2克)。 Reaction C (10 g, 19.4 mmole) and 9,9'-spirobi [fluoren]-2-ylboronic acid (8.386 g, 23.2 mmole) were placed in the reaction. In a tank, add 120 ml of toluene. Potassium carbonate (9.38 g, 67.9 mmole) was dissolved in 70 ml of deionized water and added to the reaction tank, and tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (0.672 g, 0.582 mmole) and 30 ml were added. The ethanol was heated and stirred, heated to 80 ° C and reacted overnight. After the reaction was completed, 300 ml of deionized water was added, and after stirring for 30 minutes, the stirring was stopped and allowed to stand, and the layers were separated. After removing the aqueous layer, it was purified by silica gel chromatography, and concentrated to a thick state to be added with 300 ml of hexane. The organic layer was combined and filtered to give a white solid solid compound 1-15 (~ 7.2 g).
化合物1-15 1HNMR:1H NMR(CDCl3,400MHz),δ9.8-9.7(s,1H);8.97-8.96(m,1H);8.74-8.73(m,1H);8.58-8.57(d,1H);8.4-8.35(m,3H);8.3-8.25(m,1H);8.17-8.15(m,1H);8.1-8.07(s,1H);7.94-7.39(m,17H);7.17-7.1(t,3H);7.03-7.01(s,1H);6.81-6.78(d,2H),6.5-6.4(s,1H). Compound 1-15 1 H NMR: 1 H NMR (CDCl 3 , 400 MHz), δ 9.8-9.7 (s, 1H); 8.97-8.96 (m, 1H); 8.74 - 8.73 (m, 1H); 8.58-8. d, 1H); 8.4-8.35 (m, 3H); 8.3-8.25 (m, 1H); 8.17-8.15 (m, 1H); 8.8.1-8.07 (s, 1H); 7.94-7.39 (m, 17H); 7.17-7.1 (t, 3H); 7.03-7.01 (s, 1H); 6.81-6.78 (d, 2H), 6.5-6.4 (s, 1H).
合成例11:化合物1-22之合成Synthesis Example 11: Synthesis of Compound 1-22
將3'-溴苯乙酮(3'-Bromoacetophenone)(10g,50.23mmole)與喹啉-8-硼酸(quinolin-8-ylboronic acid)(9.12g,52.75mmole)置於反應槽,加入120毫升的甲苯。將碳酸鉀(18.05g,130.6mmole)溶於70毫升的去離子水後加入反應槽,加入四(三苯基膦)鈀(Pd(PPh3)4)(1.74g,1.507mmole)及30毫升的乙醇開啟加熱及攪拌,加熱直至80℃反應並反應隔夜。待反應完後,加入300毫升的去離子水,攪拌30分鐘後停止攪拌靜置使其分層,去除水層後,用矽膠層析法純化,濃縮至濃稠,得淡黃色液體化合物E(約5.5克)。 3'-Bromoacetophenone (10 g, 50.23 mmole) and quinolin-8-ylboronic acid (9.12 g, 52.75 mmole) were placed in a reaction tank, and 120 ml was added. Toluene. Potassium carbonate (18.05 g, 130.6 mmole) was dissolved in 70 ml of deionized water and added to the reaction tank, and tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (1.74 g, 1.507 mmole) and 30 ml were added. The ethanol was heated and stirred, heated to 80 ° C and reacted overnight. After the reaction was completed, 300 ml of deionized water was added, and after stirring for 30 minutes, the stirring was stopped and allowed to stand for stratification. After removing the aqueous layer, it was purified by silica gel chromatography and concentrated to a thick color to obtain a pale yellow liquid compound E ( About 5.5 grams).
將化合物E(10g,40.737mmole)與3-溴苯甲醛(3-bromobenzaldehyde)(8.23g,44.48mmole)置於反應槽,充分除水後加入230毫升的乙醇,開啟攪拌,並添加甲醇鈉(0.655g,12.31mmole),於室溫攪拌16小時。其後,添加3-吡啶偕胺肟鹽(3-Amidinopyridinium chloride)(6.7g, 44.34mmole)與氫氧化鈉(3.22g,80.61mmole),並追加入30毫升的甲苯,打開加熱裝置,加熱直至75℃並反應隔夜。待反應完後,再以250毫升的甲苯加熱攪拌並過濾固體,得乳白色固體化合物F(約4.5克)。 Compound E (10 g, 40.737 mmole) and 3-bromobenzaldehyde (8.23 g, 44.48 mmole) were placed in a reaction tank, and after thoroughly removing water, 230 ml of ethanol was added, stirring was started, and sodium methoxide was added ( 0.655 g, 12.31 mmole), stirred at room temperature for 16 hours. Thereafter, 3-Amidinopyridinium chloride (6.7 g, 44.34 mmole) and sodium hydroxide (3.22 g, 80.61 mmole), and 30 ml of toluene were added, the heating device was turned on, heated to 75 ° C and reacted overnight. After the reaction was completed, the mixture was further stirred with 250 ml of toluene and the solid was filtered to give a white solid compound F (about 4.5 g).
將化合物F(10g,19.4mmole)與(10-苯基蒽-9基)-硼酸((10-phenylanthracen-9-yl)boronic acid)(6.36g,21.32mmole)置於反應槽,加入120毫升的甲苯。將碳酸鉀(9.38g,67.9mmole)溶於70毫升的去離子水後加入反應槽,加入四(三苯基膦)鈀(Pd(PPh3)4)(0.67g,0.582mmole)及30毫升的乙醇開啟加熱及攪拌,加熱直至80℃並隔夜反應。待反應完後,加入300毫升的去離子水,攪拌30分鐘後停止攪拌靜置使其分層,去除水層後,用矽膠層析法純化,濃縮至濃稠態加入300毫升的己烷析出,有機層合併過濾固體,得淡黃色固體化合物1-22(約3克)。 Compound F (10 g, 19.4 mmole) and (10-phenylanthracen-9-yl) boronic acid (6.36 g, 21.32 mmole) were placed in a reaction tank, and 120 ml was added. Toluene. Potassium carbonate (9.38 g, 67.9 mmole) was dissolved in 70 ml of deionized water and added to the reaction tank, and tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (0.67 g, 0.582 mmole) and 30 ml were added. The ethanol was heated and stirred, heated to 80 ° C and reacted overnight. After the reaction was completed, 300 ml of deionized water was added, and after stirring for 30 minutes, the stirring was stopped and allowed to stand, and the layers were separated. After removing the aqueous layer, it was purified by silica gel chromatography, and concentrated to a thick state to be added with 300 ml of hexane. The organic layer was combined and filtered to give a pale-yellow solid compound 1-22 (~3 g).
合成例12:化合物1-23之合成Synthesis Example 12: Synthesis of Compound 1-23
將化合物A(10g,40.737mmole)與3-溴苯甲醛(4-bromobenzaldehyde)(8.23g,44.48mmole)置於反應槽,充分除水後加入230毫升的乙醇,開啟攪拌,並添加甲醇鈉(0.655g,12.31mmole),於室溫攪拌16小時。其後,添加2-吡啶偕胺肟鹽(2-Amidinopyridinium chloride)(6.7g,44.34mmole)與氫氧化鈉(3.22g,80.61mmole),並追加入30毫升的甲苯,打開加熱裝置,加熱直至75℃並反應隔夜。待反應完後,過濾取固體,再以250毫升的甲苯加熱攪拌並過濾固體,得乳白色固體化合物G(約3.8克)。 Compound A (10 g, 40.737 mmole) and 3-bromobenzaldehyde (8.23 g, 44.48 mmole) were placed in a reaction tank, and after thoroughly removing water, 230 ml of ethanol was added, stirring was started, and sodium methoxide was added ( 0.655 g, 12.31 mmole), stirred at room temperature for 16 hours. Thereafter, 2-Amidinopyridinium chloride (6.7 g, 44.34 mmole) and sodium hydroxide (3.22 g, 80.61 mmole) were added, and 30 ml of toluene was added thereto, and the heating device was turned on and heated until 75 ° C and react overnight. After completion of the reaction, the solid was filtered, and the mixture was stirred and stirred with 250 ml of toluene, and the solid was filtered to give a white solid compound G (about 3.8 g).
將化合物G(10g,19.4mmole)與(10-苯基蒽-9基)-硼酸((10-phenylanthracen-9-yl)boronic acid)(6.36g,21.32mmole)置於反應槽,加入120毫升的甲苯。將碳酸鉀(9.38g,67.9mmole)溶於70毫升的去離子水後加入反應槽, 加入四(三苯基膦)鈀(Pd(PPh3)4)(0.67g,0.582mmole)及30毫升的乙醇開啟加熱及攪拌,加熱直至80℃並隔夜反應。待反應完後,加入300毫升的去離子水,攪拌30分鐘後停止攪拌靜置使其分層,去除水層後,用矽膠層析法純化,濃縮至濃稠態加入300毫升的己烷析出,有機層合併過濾固體,得淡黃色固體化合物1-23(約3.3克)。 Compound G (10 g, 19.4 mmole) and (10-phenylanthracen-9-yl) boronic acid (6.36 g, 21.32 mmole) were placed in a reaction tank, and 120 ml was added. Toluene. Potassium carbonate (9.38 g, 67.9 mmole) was dissolved in 70 ml of deionized water and added to the reaction tank, and tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) (0.67 g, 0.582 mmole) and 30 ml were added. The ethanol was heated and stirred, heated to 80 ° C and reacted overnight. After the reaction was completed, 300 ml of deionized water was added, and after stirring for 30 minutes, the stirring was stopped and allowed to stand, and the layers were separated. After removing the aqueous layer, it was purified by silica gel chromatography, and concentrated to a thick state to be added with 300 ml of hexane. The organic layer was combined and filtered to give a pale yellow solid compound 1-23 (~ 3.3 g).
將上述材料的物性值表示於表2中。各物性值之測定方法如下所示。 The physical property values of the above materials are shown in Table 2. The method of measuring each physical property value is as follows.
(1)熱裂解溫度(Td) (1) Thermal cracking temperature (T d )
使用熱重分析儀(Perkin Elmer,TGA 8000)進行量測,在常壓且具氮氣氣氛下,以20℃/分鐘的程序升溫速率,對製得的化合物的熱裂解性質進行量測,並將重量減小至起始重量的95%的溫度即為熱裂解溫度(Td)。 The thermogravimetric analyzer (Perkin Elmer, TGA 8000) was used for measurement, and the pyrolysis property of the obtained compound was measured at a normal temperature and nitrogen atmosphere at a programmed temperature of 20 ° C / min. The temperature at which the weight is reduced to 95% of the initial weight is the thermal cracking temperature (T d ).
(2)玻璃轉移溫度(Tg) (2) Glass transition temperature (T g )
使用示差掃描熱分析儀(DSC;Perkin Elmer,DSC 8000)以20℃/分鐘的程序升溫速率對製得的化合物進行量測。 The prepared compound was measured using a differential scanning calorimeter (DSC; Perkin Elmer, DSC 8000) at a programmed temperature rate of 20 ° C/min.
(3)最高佔據分子軌道(HOMO)之能階值 (3) The energy level of the highest occupied molecular orbital (HOMO)
另外,將化合物製成薄膜狀態,於大氣下使用光電子分光光度計(Riken Keiki,Surface Analyzer)量測其電離電位數值,將其數值進一步轉化後即為HOMO能階值。 In addition, the compound was made into a thin film state, and its ionization potential value was measured under a atmosphere using a photoelectron spectrophotometer (Riken Keiki, Surface Analyzer), and the value was further converted to a HOMO energy level value.
(4)最低未占分子軌道(LUMO)之能階值 (4) The lowest unoccupied molecular orbital (LUMO) energy level value
將上述化合物之薄膜以UV/VIS分光光度計(Perkin Elmer,Lambda 20)量測其吸收波長之邊界值(onset),將該值經轉換得能隙值,使能隙值與HOMO能階的數值相減, 即得LUMO能階。 The film of the above compound was measured by a UV/VIS spectrophotometer (Perkin Elmer, Lambda 20) for the onset of the absorption wavelength, and the value was converted into an energy gap value to enable the energy gap value and the HOMO energy level. The value is subtracted, That is, the LUMO energy level is obtained.
(5)三重態能量值(ET) (5) Triplet energy value (E T )
使用螢光光譜儀(Perkin Elmer,LS 55)於溫度77K下量測發光光譜,再經由計算,可得ET。 The luminescence spectrum was measured using a fluorescence spectrometer (Perkin Elmer, LS 55) at a temperature of 77 K, and then E T was obtained by calculation.
實施例1:有機電激發光元件之製造Example 1: Fabrication of Organic Electroluminescent Devices
於基板載入蒸鍍系統使用前,先以溶劑及紫外線臭氧清洗基板進行脫脂。之後,將基板傳送至真空沉積室,於基板之頂部沉積所有層。依第2圖所示之各層係由加熱的蒸鍍舟(boat)在約10-6托之真空度依序沉積:a)電洞注入層,厚度20奈米,包含摻雜有9%p型電性傳導摻質之HTM,其中,該p型電性傳導摻質係購自上海瀚豐化工有限公司,且該HTM係購自Merck & Co.,Inc.;b)電洞傳輸層,厚度170奈米,HTM;c)激子阻擋層,厚度10奈米,HT(昱鐳光電製備); d)發光層,厚度25奈米,包含摻雜有4%體積比BD之EBH,其中,BD及EBH為昱鐳光電製備;e)電子傳輸層,厚度25奈米,包含化合物1-1及摻雜之喹啉鋰(Liq,昱鐳光電製備),體積比為1:1;f)電子注入層,厚度0.5奈米,氟化鋰(LiF);及g)陰極,厚度約180奈米,包含A1。 Before the substrate is loaded into the vapor deposition system, the substrate is first degreased with solvent and ultraviolet ozone. Thereafter, the substrate is transferred to a vacuum deposition chamber, and all layers are deposited on top of the substrate. The layers shown in Figure 2 are sequentially deposited by a heated vapor boat at a vacuum of about 10 -6 Torr: a) a hole injection layer, 20 nm thick, containing 9% p. Type electrically conductive dopant HTM, wherein the p-type electrically conductive dopant is purchased from Shanghai Yufeng Chemical Co., Ltd., and the HTM is purchased from Merck & Co., Inc.; b) hole transport layer, Thickness 170 nm, HTM; c) exciton blocking layer, thickness 10 nm, HT (manufactured by 昱 radium photoelectric); d) luminescent layer, thickness 25 nm, containing EBH doped with 4% by volume BD, wherein , BD and EBH are prepared by 昱 radium photoelectric; e) electron transport layer, thickness 25 nm, containing compound 1-1 and doped quinoline lithium (Liq, 昱 radium photoelectric preparation), volume ratio is 1:1; f An electron injecting layer having a thickness of 0.5 nm, lithium fluoride (LiF), and g) a cathode having a thickness of about 180 nm and containing A1.
元件結構可表示如:ITO/HTM:p型電性傳導摻質(20奈米)/HTM(170奈米)/HT(10奈米)/EBH:BD(25奈米)/化合物1-1:Liq(25奈米)/LiF(0.5奈米)/Al(180奈米)。 The structure of the element can be expressed as: ITO/HTM: p-type electrically conductive dopant (20 nm) / HTM (170 nm) / HT (10 nm) / EBH: BD (25 nm) / compound 1-1 : Liq (25 nm) / LiF (0.5 nm) / Al (180 nm).
於沉積形成上述各層後,該元件自沉積室傳送至乾燥箱中,隨即以UV可固化環氧樹脂及含有吸濕劑之玻璃蓋板進行封裝。該有機電激發光元件具有9平方毫米之發光區域。 After deposition to form the above layers, the component is transferred from the deposition chamber to a dry box and then encapsulated with a UV curable epoxy resin and a glass cover containing a moisture absorbent. The organic electroluminescent device has a light-emitting area of 9 square millimeters.
實施例2至7:有機電激發光元件之製造Examples 2 to 7: Fabrication of organic electroluminescent elements
除將實施例1中電子傳輸層之化合物1-1各別置換為化合物1-2、1-3、1-5、1-10、1-11及1-15,實施例2、實施例3、實施例4、實施例5、實施例6及實施例7係如實施例1之層結構。 Except that the compound 1-1 of the electron transport layer in Example 1 was replaced with the compounds 1-2, 1-3, 1-5, 1-10, 1-11 and 1-15, respectively, Example 2, Example 3 Example 4, Example 5, Example 6 and Example 7 are layer structures as in Example 1.
比較實施例1:有機電激發光元件之製造Comparative Example 1: Fabrication of organic electroluminescent elements
將有機電激發光元件置造成結構類似實施例1的層結構,除了將實施例1中電子傳輸層之化合物1-1置換為化合物EET09,該有機電激發光元件結構可表示如:ITO/HTM:p dopant(20奈米)/HTM(170奈米)/HT(10奈米)/EBH:BD(25奈米)/化合物EET09:Liq(25奈米)/LiF(0.5奈米)/Al(180奈米)。 The organic electroluminescent device was placed in a layer structure similar to that of Example 1, except that the compound 1-1 of the electron transporting layer in Example 1 was replaced with the compound EET09, and the organic electroluminescent device structure could be represented by, for example, ITO/HTM. : p dopant (20 nm) / HTM (170 nm) / HT (10 nm) / EBH: BD (25 nm) / compound EET09: Liq (25 nm) / LiF (0.5 nm) / Al (180 nm).
其中,該化合物EET09如日本專利第2011003793A號所述。 Among them, the compound EET09 is as described in Japanese Patent No. 2011003793A.
上述製成之有機電激發光元件之電激發光性質均使用定電流源(KEITHLEY 2400 Source Meter,made by Keithley Instruments,Inc.,Cleveland,Ohio)及光度計(PHOTO RESEARCH SpectraScan PR 650,made by Photo Research,Inc.,Chatsworth,Calif.)於室溫下測量其發光性質,以比較實施例之有機電激發光元件為基準(標準值為1),將其驅動電壓、發光效率及LT95之值列示於表3。其中,LT95值之定義為亮度水平降至相對於初始亮度的95%的水平所消耗的時間,係作為評估有機電激發光元件之使用壽命或穩定性的衡量標準。 The electroluminescent properties of the above-mentioned organic electroluminescent device are all based on a constant current source (KEITHLEY 2400 Source Meter, made by Keithley Instruments, Inc., Cleveland, Ohio) and a photometer (PHOTO RESEARCH SpectraScan PR 650, made by Photo) Research, Inc., Chatsworth, Calif.) measured its luminescent properties at room temperature, based on the organic electroluminescent device of the comparative example (standard value is 1), and its driving voltage, luminous efficiency and value of LT95 are listed. Shown in Table 3. Among them, the LT95 value is defined as the time taken for the brightness level to fall to a level of 95% relative to the initial brightness as a measure of the service life or stability of the organic electroluminescent element.
如上所述,於可接受的驅動電壓及發光效率的損失範圍內,可見包含本發明之具式(I)結構之經喹啉取代之二苯基嘧啶化合物之有機電激發光元件展現良好耐熱性並顯著改善其使用壽命,因此,本發明之有機電激發光元件適用於車用顯示器等應用領域,且具有極高之技術價值。 As described above, it is seen that the organic electroluminescent device comprising the quinoline-substituted diphenylpyrimidine compound having the structure of the formula (I) of the present invention exhibits good heat resistance within a range of acceptable driving voltage and luminous efficiency loss. The service life of the organic electroluminescent device of the present invention is suitable for applications such as vehicle displays, and has extremely high technical value.
上述實施例僅為例示性說明,而非用於限制本發明。任何熟習此項技藝之人士均可在不違背本發明之精神及範疇下,對上述實施例進行修飾與改變。因此,本發明之權 利保護範圍係由本發明所附之申請專利範圍所定義,只要不影響本發明之效果及實施目的,應涵蓋於此公開技術內容中。 The above embodiments are merely illustrative and are not intended to limit the invention. Modifications and variations of the above-described embodiments can be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the right of the present invention The scope of protection is defined by the scope of the patent application attached to the present invention, and should be included in the technical scope of the disclosure as long as it does not affect the effects and the purpose of the present invention.
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