CN103249800A - Novel compounds for organic electronic material and organic electroluminescent device using the same - Google Patents
Novel compounds for organic electronic material and organic electroluminescent device using the same Download PDFInfo
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- CN103249800A CN103249800A CN2011800586027A CN201180058602A CN103249800A CN 103249800 A CN103249800 A CN 103249800A CN 2011800586027 A CN2011800586027 A CN 2011800586027A CN 201180058602 A CN201180058602 A CN 201180058602A CN 103249800 A CN103249800 A CN 103249800A
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- 0 *c(cc1)cc(c2c3ccc4ccccc24)c1[n]3-c(cc1)ccc1-c1c(*)ccc(-[n](c2ccccc22)c3c2c(cccc2)c2cc3)c1 Chemical compound *c(cc1)cc(c2c3ccc4ccccc24)c1[n]3-c(cc1)ccc1-c1c(*)ccc(-[n](c2ccccc22)c3c2c(cccc2)c2cc3)c1 0.000 description 4
- VKQJZAYTLAEXJW-UHFFFAOYSA-N CC(C)(c(cccc1)c1-c1c2)c1cc(c1c3cccc1)c2[n]3-c(cc1)ccc1-c1nc(cccc2)c2c(-c(cc2)ccc2-c2cc3ccccc3cc2)n1 Chemical compound CC(C)(c(cccc1)c1-c1c2)c1cc(c1c3cccc1)c2[n]3-c(cc1)ccc1-c1nc(cccc2)c2c(-c(cc2)ccc2-c2cc3ccccc3cc2)n1 VKQJZAYTLAEXJW-UHFFFAOYSA-N 0.000 description 1
- UCTBRNHPKITCHL-UHFFFAOYSA-N CC(C)(c1ccccc1-c1c2)c1cc(c1c3cccc1)c2[n]3-c1ccc(C)cc1 Chemical compound CC(C)(c1ccccc1-c1c2)c1cc(c1c3cccc1)c2[n]3-c1ccc(C)cc1 UCTBRNHPKITCHL-UHFFFAOYSA-N 0.000 description 1
- JVZPCKWGKZYQRO-UHFFFAOYSA-N CC(C)(c1ccccc1-c1ccc2c3c4cccc3)c1c2[n]4-c1ccc(C)cc1 Chemical compound CC(C)(c1ccccc1-c1ccc2c3c4cccc3)c1c2[n]4-c1ccc(C)cc1 JVZPCKWGKZYQRO-UHFFFAOYSA-N 0.000 description 1
- SYMCRQGRGTYBCP-UHFFFAOYSA-N CC(C1)C=CC(C(C)(C)c2c3)=C1c2ccc3-c1nc(C(C=C2)=CCC2(C)[n](c2c3cccc2)c2c3c(cccc3)c3cc2)nc2c1cccc2 Chemical compound CC(C1)C=CC(C(C)(C)c2c3)=C1c2ccc3-c1nc(C(C=C2)=CCC2(C)[n](c2c3cccc2)c2c3c(cccc3)c3cc2)nc2c1cccc2 SYMCRQGRGTYBCP-UHFFFAOYSA-N 0.000 description 1
- JVRWIGODGORMCI-UHFFFAOYSA-N CC1(C)c(cc(cc2)-[n]3c4ccc(cccc5)c5c4c4c3cccc4)c2-c2ccc(C)cc12 Chemical compound CC1(C)c(cc(cc2)-[n]3c4ccc(cccc5)c5c4c4c3cccc4)c2-c2ccc(C)cc12 JVRWIGODGORMCI-UHFFFAOYSA-N 0.000 description 1
- YRWGYNCNPFCMFZ-UHFFFAOYSA-N CC1C2C=CC(c(cc3)ccc3-c3nc(C(C=C4)=CCC4(C)[n]4c(c(C5(C)C)c(cc6)-c7c5cccc7)c6c5c4cccc5)nc4c3cccc4)=CC2(C)C=CC1 Chemical compound CC1C2C=CC(c(cc3)ccc3-c3nc(C(C=C4)=CCC4(C)[n]4c(c(C5(C)C)c(cc6)-c7c5cccc7)c6c5c4cccc5)nc4c3cccc4)=CC2(C)C=CC1 YRWGYNCNPFCMFZ-UHFFFAOYSA-N 0.000 description 1
- GDNWYSQTJTXYMU-UHFFFAOYSA-N Cc(cc1c2ccc(cccc3)c3c22)ccc1[n]2-c1ccccc1 Chemical compound Cc(cc1c2ccc(cccc3)c3c22)ccc1[n]2-c1ccccc1 GDNWYSQTJTXYMU-UHFFFAOYSA-N 0.000 description 1
- AVPLCPIXXJOBHG-UHFFFAOYSA-N Cc(cc1c2ccccc22)ccc1[n]2-c1ccccc1 Chemical compound Cc(cc1c2ccccc22)ccc1[n]2-c1ccccc1 AVPLCPIXXJOBHG-UHFFFAOYSA-N 0.000 description 1
- DGISNPACYSVIPI-UHFFFAOYSA-N I[n](c1c2cccc1)c(cc1)c2c2c1c1ccccc1[o]2 Chemical compound I[n](c1c2cccc1)c(cc1)c2c2c1c1ccccc1[o]2 DGISNPACYSVIPI-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- Electroluminescent Light Sources (AREA)
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Abstract
Provided are novel compounds for an organic electronic material and an organic electroluminescent device using the same. Because the compound for an organic electronic material disclosed herein exhibits high electron transport efficiency and thus prevents crystallization upon manufacturing a device, and also facilitates the formation of a layer, thus improving current properties of the device. Thereby, OLED devices having improved power efficiency as well as reduced operating voltage can be manufactured.
Description
Technical field
The present invention relates to for the new compound of organic electronic material and the organic electroluminescence device that comprises this compound.
Technical background
In display device, the electroluminescent of self-emission display device (EL) device is preferred, because they provide contrast gradient and the quick speed of response of wide visual angle, excellence.Eastman Kodak Co (Eastman Kodak) has at first developed a kind of organic EL device in 1987, this device uses low molecular weight aromatic diamines and aluminum complex as the material [Appl.Phys.Lett.51,913,1987] that forms electroluminescence layer.
When electric charge is injected into the organic layer that is formed between electron injection electrode (negative electrode) and the hole injecting electrode (anode), form the pairing of electronics and hole, when electron-hole pair is buried in oblivion, organic EL device luminous (phosphorescence or fluorescence).Organic EL device is being about under the voltage of 10V, with 100-10, and 000cd/m
2The brightness polarized light-emitting, it adopts fluorescent material simply, thereby luminous to the red color spectrum range in blueness.Described equipment can form at flexible transparent base material (for example plastics), also can compare operation under the low voltage (10V or lower) of plasma display panel or inorganic EL indicating meter, can consume less power consumption and have excellent color.
Determined to comprise luminous efficiency, most important factor in interior organic EL device performance such as life-span is electroluminescent material, several characteristics that also need following electroluminescent material, the low decomposability when comprising high mobility, the vacuum moulding machine in high-fluorescence quantum yield, electronics and the hole of solid phase and form uniform and stable film.
Electroluminescent organic material can broadly be divided into high molecular weight material and low molecular weight material, and described low molecular weight material can comprise the metal complex compounds and metal-free pure electroluminescent organic material aspect molecular structure.This known based electroluminescent material for example has: such as the chelant complex of three (oxine) aluminum complex etc., coumarin derivatives, tetraphenylbutadiene derivative, diphenylethyllene arylene derivatives, oxadiazole derivative etc., it is reported that they can launch visible light in blueness to red color range.
In order to realize full color OLED indicating meter, need to use these three kinds of electroluminescent materials of RGB.The RGB electroluminescent material that exploitation has high-level efficiency and long service live is important for the overall characteristic that improves organic EL device.Electroluminescent material comprises substrate material and for the dopant material of functional purpose.Usually, known device with very excellent electroluminescence characters has such structure, and wherein, matrix and doping agent mix to form electroluminescence layer.At present, exploitation has high-level efficiency and long-life organic EL device is just becoming a urgent task.Especially, consider the medium-sized extremely required electroluminescence characters of large-scale oled panel, it is urgent developing the non-material that is often better than conventional electroluminescent material, and therefore, the development of substrate material is considered to very important.For this reason, in solid phase, play solvent action and the substrate material fluorescence of playing an important role is highly purified in energy transmission, and must have and to realize vacuum-deposited suitable molecular weight.Similarly; glass transition temp and heat decomposition temperature are should be enough high, guaranteeing obtaining required thermostability and high electrochemical stability of long lifetime, and should easily form amorphous thin film; and with the bounding force of the material of other adjacent layerss must be good, do not answer between genetic horizon mobile.
Using doping techniques to make under the situation of organic EL device, the ratio that energy is transferred to doping agent from the substrate molecule of excited state is not 100%, and substrate material and doping agent all can be luminous.Specifically, under the situation of red electroluminescent device, the emission wavelength scope of substrate material is more high-visible than doping agent, because substrate material sends unintelligible visible light, so the purity of color variation.In practice, need improve life-span and the weather resistance of EL.
At present, known CBP is the substrate material that is widely used as phosphor material most.Reported the efficient OLED that uses the hole blocking layer that comprises BCP, BAlq etc.Pioneer Electronic Corp. (Japan) etc. has reported and has used the BAlq derivative as the high-performance OLED of matrix.
Although these traditional materials provide good electroluminescence characters, they have some defectives, and as degrading in the high-temperature vacuum deposition process, this is because they have the thermostability of low second-order transition temperature and difference.Because the power efficiency of OLED determined by (π/voltage) * current efficiency, thus power efficiency and voltage be inversely proportional to, thereby so power efficiency should the higher power loss that reduces OLED.In fact, use the OLED of phosphor material to provide than the much higher current efficiency (cd/A) of OLED of using fluorescent material.But, when current material when for example BAlq, CBP etc. are as the matrix of phosphor material, to compare and use the OLED of fluorescent material not having clear superiority aspect the power efficiency (lm/W), this is because driving voltage is higher.In addition, the life-span of OLED device is also unsatisfactory, therefore needs to develop a kind of more high performance more stable substrate material that has.
Summary of the invention
Technical problem
Therefore, the present invention is directed to the problem that prior art exists, an object of the present invention is to provide the compound for organic electronic material, it has main chain, thereby can realize better luminous efficiency and the device lifetime with suitable chromaticity coordinates than traditional material.
Another object of the present invention provides has high-level efficiency and long-life organic electroluminescence device, and it uses the compound that is used for as the organic electronic compound of electroluminescent material.
Technical scheme
A kind of compound of representing for the following Chemical formula 1 of organic electronic material is provided, and the organic electroluminescence device that uses this compound.Because the compound for organic electronic material of the present invention has superior luminous efficiency and good life properties, it can be used for making the OLED device, and this device has very superior working life and because the low power consumption that improved power efficiency causes.
Chemical formula 1
In Formula I, L
1And L
2Represent singly-bound, (C6-C30) arylidene or (C3-C30) heteroarylidene independently;
X
1And X
2Represent CR independently
4Or N, wherein X
1And X
2Not all be CR
4
Ring A represents monocycle or many ring (C6-C30) aromatic rings;
R
1To R
4Represent hydrogen independently, deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano group, (C3-C30) cycloalkyl, 5-unit to 7-unit Heterocyclylalkyl, (C2-C30) thiazolinyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxyl group, (C6-C30) aryloxy, (C3-C30) heteroaryl, (C6-C30) aryl (C1-C30) alkyl, (C6-C30) arylthio, list or two (C1-C30) alkylamino, list or two (C6-C30) arylamino, three (C1-C30) alkyl silyl, two (C1-C30) alkyl (C6-C30) aryl silyl, three (C6-C30) aryl silyl, nitro or hydroxyl;
L
1And L
2Arylidene and heteroarylidene, the aromatic ring of ring A, and R
1To R
4Alkyl, cycloalkyl, Heterocyclylalkyl, thiazolinyl, alkynyl, aryl and heteroaryl also can further be replaced by one or more substituting groups independently, and described substituting group is selected from: deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano group, (C3-C30) cycloalkyl, 5-unit to 7-unit Heterocyclylalkyl, (C2-C30) thiazolinyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxyl group, (C6-C30) aryloxy, (C3-C30) heteroaryl, (C1-C30) (C3-C30) heteroaryl of alkyl replacement, (C6-C30) (C3-C30) heteroaryl of aryl replacement, (C6-C30) aryl (C1-C30) alkyl, (C6-C30) arylthio, list or two (C1-C30) alkylamino, list or two (C6-C30) arylamino, three (C1-C30) alkyl silyl, two (C1-C30) alkyl (C6-C30) aryl silyl, (C1-C30) alkyl two (C6-C30) aryl silyl, three (C6-C30) aryl silyl, nitro and hydroxyl;
Described heteroarylidene, Heterocyclylalkyl and heteroaryl comprise one or more B of being selected from, N, O, S, P (=O), the heteroatoms of Si and P; And
Except R
2-L
2-* is the situation of hydrogen.
Term used herein " alkyl ", " alkoxyl group " and other substituting groups that contains " alkyl " part comprise straight chain and branched material, and " cycloalkyl " comprises the polynuclear hydrocarbon ring, for example is with or without substituent adamantyl or is with or without substituent (C7-C30) bicyclic alkyl and monocyclic hydrocarbon ring.Term used herein " aryl " refers to by removing the organic group that hydrogen atom obtains from aromatic hydrocarbon, comprises 4 yuan to 7 yuan, is preferably monocycle or the condensed ring of 5 yuan or 6 yuan, even can also comprise the structure by singly linked a plurality of aryl.Their object lesson includes but not limited to, phenyl, naphthyl, xenyl (biphenyl), anthryl, indenyl, fluorenyl, phenanthryl (phenanthryl), benzo [9,10] phenanthryl (triphenylenyl), pyrenyl,
Base (perylenyl),
Base (chrysenyl), naphthacenyl (naphthacenyl), fluoranthene base (fluoranthenyl) etc.Described naphthyl comprises 1-naphthyl and 2-naphthyl, and described anthryl comprises 1-anthryl, 2-anthryl and 9-anthryl, and described fluorenyl comprises 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl.Term used herein " heteroaryl " expression comprise 1-4 be selected from B, N, O, S, P (=O), the heteroatoms of Si and P is as the aromatic ring frame atom, and other aromatic ring frame atoms aromatic yl group that is carbon.It can be to condense 5 yuan of obtaining or 6 yuan of bicyclic heteroaryls or polyheteroaromatic with one or more phenyl ring, and can be fractional saturation.In the present invention, " heteroaryl " comprises one or more heteroaryls by singly linked structure.Described heteroaryl comprises the divalence heteroaryl, wherein the heteroatoms in the ring can oxidized or quaternized formation for example N-oxide compound or quaternary ammonium salt.Their object lesson includes, but are not limited to, and bicyclic heteroaryl is furyl, thienyl, pyrryl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl group, isothiazolyl, isoxazolyl, oxazolyl, oxadiazole base, triazinyl, tetrazine base, triazolyl, tetrazyl, furazan base (furazanyl), pyridyl, pyrazinyl, pyrimidyl, pyridazinyl etc. for example; Polyheteroaromatic is benzofuryl (benzofuranyl) for example, benzothienyl, isobenzofuran-base, benzimidazolyl-, benzothiazolyl, the benzisothiazole base, benzoisoxazole base benzoxazolyl, pseudoindoyl, indyl, indazolyl, the diazosulfide base, quinolyl, isoquinolyl, cinnolines base (cinnolinyl), quinazolyl, quinoxalinyl (quinoxalinyl), carbazyl, phenanthridinyl (phenanthridinyl) or benzo dioxolyl (benzodioxolyl) etc.; And N-oxide compound (for example pyridyl N-oxide compound, quinolyl N-oxide compound); Or its quaternary ammonium salt etc.
Term used herein " (C1-C30) alkyl " comprises (C1-C20) alkyl or (C1-C10) alkyl, and term " (C6-C30) aryl " comprises (C6-C20) aryl or (C6-C12) aryl.Term " (C3-C30) heteroaryl " comprises (C3-C20) heteroaryl or (C3-C12) heteroaryl, and term " (C3-C30) cycloalkyl " comprises (C3-C20) cycloalkyl or (C3-C7) cycloalkyl.Term " (C2-C30) alkenyl or alkynyl " comprises (C2-C20) alkenyl or alkynyl or (C2-C10) alkenyl or alkynyl.
Specifically, L
1And L
2Represent singly-bound, (C6-C30) arylidene or (C3-C30) heteroarylidene independently; X
1And X
2Represent CR independently
4Or N, wherein X
1And X
2Can not all be CR
4Ring A represents monocycle or many ring (C6-C30) aromatic rings; R
1To R
4Represent hydrogen, deuterium, (C6-C30) aryl or (C3-C30) heteroaryl independently; L
1And L
2Arylidene and heteroarylidene, the ring A aromatic ring and R
1To R
4Aryl and heteroaryl one or more substituting groups that can be independently be selected from down group further replace: (C3-C30) heteroaryl that (C3-C30) heteroaryl that deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, (C6-C30) aryl, (C3-C30) heteroaryl, (C1-C30) alkyl replace, (C6-C30) aryl replace and (C6-C30) aryl (C1-C30) alkyl.
More particularly,
Be
Perhaps
R
aAnd R
bExpression (C1-C7) alkyl or (C6-C12) aryl independently;
R
cTo R
eRepresent (C3-C30) heteroaryl that hydrogen, deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, (C6-C30) aryl, (C3-C30) heteroaryl, (C1-C30) alkyl replaces, (C3-C30) heteroaryl that (C6-C30) aryl replaces and (C6-C30) aryl (C1-C30) alkyl independently;
R
1-L
1-* and R
2-L
2-* represents hydrogen independently or is selected from following structure, except R
2-L
2-* is the situation of hydrogen:
More specifically, the compound that is used for organic electronic material of the present invention can be enumerated as following compound, but they are not construed as limiting the present invention:
The compound that is used for organic electronic material of the present invention can prepare by following proposal 1, but is not limited thereto, and can use known methodology of organic synthesis to prepare.
[scheme 1]
In scheme 1, the X of Chemical formula 1
1, X
2, L
1, L
2, ring A and R
1To R
3Definition identical with the definition in the Chemical formula 1; And X represents halogen.
A kind of organic electroluminescence device is provided, and it comprises first electrode; Second electrode; And one or more layers organic layer between described first electrode of insertion and second electrode, wherein said organic layer comprises one or more compounds that are used for organic electronic material of Chemical formula 1.This organic layer comprises electroluminescence layer, and the compound that is used for organic electronic material of Chemical formula 1 is as the substrate material of electroluminescence layer.
In electroluminescence layer, when the compound that is used for organic electronic material of Chemical formula 1 is used as matrix, can comprise one or more phosphorescent dopants.Be used for the not concrete restriction of phosphorescent dopants of organic electroluminescence device of the present invention, but the optional compound of representing from following Chemical formula 2:
Chemical formula 2
M
1L
101L
102L
103
In Chemical formula 2, M
1Be the metal that is selected from the periodic table of elements the 7th family, the 8th family, the 9th family, the 10th family, the 11st family, the 13rd family, the 14th family, the 15th family and the 16th family, ligand L
101, L
102, and L
103Be independently selected from following structure:
Wherein, R
201To R
203Represent that independently hydrogen, deuterium, halogen replacement or unsubstituted (C1-C30) alkyl, (C1-C30) alkyl replace or unsubstituted (C6-C30) aryl or halogen;
R
204To R
219Represent hydrogen independently, deuterium, replace or unsubstituted (C1-C30) alkyl, replace or unsubstituted (C1-C30) alkoxyl group, replace or unsubstituted (C3-C30) cycloalkyl, replace or unsubstituted (C2-C30) thiazolinyl, replace or unsubstituted (C6-C30) aryl, replace or unsubstituted list-(C1-C30) alkylamino or replacement or unsubstituted two-(C1-C30) alkylaminos, replace or unsubstituted list-(C6-C30) arylamino or replacement or unsubstituted two-(C6-C30) arylaminos, SF5, replace or unsubstituted three (C1-C30) alkyl silyl, replace or unsubstituted two (C1-C30) alkyl (C6-C30) aryl silyl, replace or unsubstituted three (C6-C30) aryl silyl, cyano group or halogen;
R
220To R
223Represent independently that hydrogen, deuterium, halogen replace or unsubstituted (C1-C30) alkyl or (C1-C30) alkyl replace or unsubstituted (C6-C30) aryl;
R
224And R
225Represent hydrogen, deuterium, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or halogen, perhaps R independently
224And R
225(C3-C12) alkylidene group that can be by being with or without condensed ring or have or do not have (C3-C12) alkenylene of condensed ring to be connected to form alicyclic ring and monocycle or many cyclophanes ring;
R
226Expression replaces or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C5-C30) heteroaryl or halogen;
R
227To R
229Represent hydrogen, deuterium, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl or halogen independently; And
Q represents
Perhaps
R wherein
231To R
242Represent that independently hydrogen, deuterium, halogen replace or unsubstituted (C1-C30) alkyl, (C1-C30) alkoxyl group, halogen, replacement or unsubstituted (C6-C30) aryl, cyano group or replacement or unsubstituted (C5-C30) cycloalkyl, perhaps they can be connected to adjacent substituting group by alkylidene group or alkenylene and form volution or condensed ring, perhaps can be connected to R by alkylidene group or alkenylene
207Or R
208Form saturated or unsaturated condensed ring.
The phosphorescent dopants compound of Chemical formula 2 can be by the exemplary expression of following compound, but is not limited thereto.
Organic electroluminescence device of the present invention comprises the compound for the Chemical formula 1 of organic electronic material, also can comprise the compound that one or more are selected from aromatic amine compound or styryl aromatic amine compound.The object lesson of described aryl amine compound or styryl aromatic amine compound discloses as described in 2010-0064712 number or 2010-0048447 number as Korean Patent, but is not limited thereto.
In organic electroluminescence device of the present invention, except being used for the compound of organic electronic material of Chemical formula 1, organic layer can comprise that also one or more are selected from the organo-metallic of the periodic table of elements the 1st family, the 2nd family, period 4 and period 5 transition metal, metal or the complex compound of lanthanide series metal and d-transition element.Described organic layer can comprise electroluminescence layer and charge generation layer.
In addition, except above-mentioned compound for organic electronic material, described organic layer can comprise simultaneously that also one or more comprise the organic electro luminescent layer of the compound of red-emitting, green glow and blue light, to realize the organic electroluminescence device of emission white light.The example of the compound of red-emitting, green glow and blue light can be that for example Korean Patent discloses 2010-0064712 number or 2010-0048447 number described compound, but is not limited thereto.
In organic electroluminescence device of the present invention, the layer (hereinafter referred to as " upper layer ") that is selected from chalcogenide layer, metal halide and metal oxide layer can be arranged on the internal surface of one or two electrode in the electrode pair.Specifically, the metal chalcogenide of silicon and aluminium (comprising oxide compound) layer can place on the anode surface of electroluminescent medium layer, and metal halide or metal oxide layer can place on the cathode surface of described electroluminescent medium layer.Thereby obtain job stability.For example, chalkogenide can be SiO
x(1≤x≤2), AlO
x(1≤x≤1.5), SiON, SiAlON etc.For example, metal halide can be LiF, MgF
2, CaF
2, rare earth metal fluorochemical etc.For example, metal oxide can be Cs
2O, Li
2O, MgO, SrO, BaO, CaO etc.
In organic electroluminescence device of the present invention, the mixing zone of electric transmission compound and reductibility doping agent also preferably is set, perhaps the mixing zone of hole transport compound and oxidisability doping agent at least one surface of prepared electrode pair.In this case, because the electric transmission compound is reduced into negatively charged ion, thereby promotes electronics from the mixing zone injection and be transferred to electroluminescent medium.In addition, because the oxidized formation positively charged ion of hole transport compound, thereby promote the hole from the mixing zone injection and be transferred to electroluminescent medium.Preferred oxidisability doping agent comprises various Lewis acids and acceptor compound.Preferred reductibility doping agent comprises basic metal, alkali metal compound, alkaline-earth metal, rare earth metal and composition thereof.In addition, the organic electroluminescence device that emits white light with two-layer or more multi-layered electroluminescence layer can use the reductibility dopant layer to prepare as charge generation layer.
Useful effect of the present invention
According to the present invention, the compound of organic electronic material can be used for making the operating voltage with improved power efficiency and reduction, shows the OLED device of good luminous efficiency simultaneously.
The embodiment of invention
Hereinafter further describe the compound of organic electronic material of the present invention as an example with reference to representative compounds of the present invention, and preparation method thereof with the electroluminescent properties of device.But these embodiment only are used for describing the embodiment purpose, are not intended to limit the scope of the invention.
[preparation example 1] preparation compound 1
The preparation of compound 1-1
1-bromo-oil of mirbane 10g (49.5mmol) and 1-naphthalene boronic acids 10.2g (59.3mmol) are dissolved in the mixture that comprises 200mL toluene, 50mL ethanol and 50mL water, and add Pd (PPh
3)
42.9g (2.5mmol) with salt of wormwood 20.5g (148.3mmol).This mixture stirred 5 hours at 120 ℃, and was cooled to room temperature, with 40mL aqueous ammonium chloride solution termination reaction.Extract this mixture with 500mL EA, the organic layer that obtains cleans with 100mL distilled water.Use anhydrous MgSO
4Dry organic layer, organic solvent is removed in decompression.Subsequently, with silica gel column chromatography chromatographic separation gained solid, obtain compound 1-1 (10g, 81%).
The preparation of compound 1-2
1-1 is dissolved among 1, the 2-dichlorobenzene 100mL with 10g (40.1mmol) compound, and adds triethoxy phosphine 100mL.This reaction mixture stirred 20 hours at 150 ℃, was cooled to room temperature then, used underpressure distillation to remove solvent, and namely 1,2-dichlorobenzene and triethoxy phosphine.With 300mL EA extraction residual organic matter matter, the organic layer that obtains cleans with 40mL distilled water.Use anhydrous MgSO
4Dry organic layer, organic solvent is removed in decompression.Subsequently, with silica gel column chromatography chromatographic separation gained solid, obtain compound 1-2 (7g, 80%).
The preparation of compound 1-3
1-2 is dissolved among the 150mL DMF with 7g (32.2mmol) compound, and adds NBS5.74g (32.2mmol).This mixture at room temperature stirred 12 hours.Subsequently, with 30mL saturated aqueous sodium thiosulfate termination reaction, with 200mL EA extraction mixture, the organic layer that obtains cleans with 20mL distilled water.Use anhydrous MgSO
4Dry organic layer, organic solvent is removed in decompression.With silica gel column chromatography chromatographic separation gained solid, obtain compound 1-3 (9g, 94%).
The preparation of compound 1-4
9g (30.4mmol) compound 1-3 and iodobenzene 8.8mL (61mmol) are dissolved in the 150mL toluene, and add CuI2.9g (15.2mmol), 1 1mL (15.2mmol) and cesium carbonate 29.7g (91.2mmol).This mixture refluxed 20 hours, and was cooled to room temperature, with 10% aqueous hydrochloric acid termination reaction.Extract this mixture with 300mL EA, the organic layer that obtains cleans with 40mL distilled water.Use anhydrous MgSO
4Dry organic layer, organic solvent is removed in decompression.With silica gel column chromatography chromatographic separation gained solid, obtain compound 1-4 (8.5g, 75%).
The preparation of compound 1-5
1-4 is dissolved among the 120mL THF with 10g (26.9mmol) compound, and this solution is cooled to-78 ℃.Add 13mL n-BuLi(2.5M at-78 ℃, in hexane).This mixture stirred 1 hour at-78 ℃, and added 4.5mL trimethoxy borine.Mixture stirred 2 hours, with 30mL aqueous ammonium chloride solution termination reaction.Extract this mixture with 300mL EA, the organic layer that obtains cleans with 50mL distilled water.Use anhydrous MgSO
4Dry organic layer, organic solvent is removed in decompression.With the separating obtained solid of recrystallization, obtain compound 1-5 (6.7g, 74%).
The preparation of compound 1-6
1,4-dibromobenzene 110g (466mmol) and 1-naphthalene boronic acids 40g (233mmol) are dissolved in the mixture that comprises 2L toluene, 500mL ethanol and 500mL water, and add Pd (PPh
3)
413.4g (11.6mmol) with yellow soda ash 74g (698mmol).This mixture stirred 5 hours at 120 ℃, and was cooled to room temperature, with 500mL aqueous ammonium chloride solution termination reaction.Extract this mixture with 3L EA, the organic layer that obtains cleans with 1L distilled water.Use anhydrous MgSO
4Dry organic layer, organic solvent is removed in decompression.Subsequently, with filtered through silica gel and the separating obtained solid of recrystallization, obtain compound 1-6 (50g, 50%).
The preparation of compound 1-7
1-6 is dissolved among the 1L THF with 60g (0.21mol) compound, and this solution is cooled to-78 ℃.Add 102mL n-BuLi(2.5M at-78 ℃, in hexane).This mixture stirred 1 hour at-78 ℃, and added 35.1mL B (OMe)
3Mixture stirred 2 hours, with 300mL aqueous ammonium chloride solution termination reaction.Extract this mixture with 2L EA, the organic layer that obtains cleans with 500mL distilled water.Use anhydrous MgSO
4Dry organic layer, organic solvent is removed in decompression.Use the separating obtained solid of recrystallization subsequently, obtain compound 1-7 (34g, 65%).
The preparation of compound 1-8
2,4-, two chloro-quinazoline 27.1g (136mmol) and 33.8g (136mmol) compound 1-7 are dissolved in the mixture that comprises 800mL toluene, 200mL ethanol and 200mL water, and add Pd (PPh
3)
46.3g (5.45mmol) with yellow soda ash 43.3g (409mmol).This mixture stirred 5 hours at 120 ℃, and was cooled to room temperature, with 200mL aqueous ammonium chloride solution termination reaction.Extract this mixture with 1.5L EA, the organic layer that obtains cleans with 500mL distilled water.Use anhydrous MgSO
4Dry organic layer, organic solvent is removed in decompression.Subsequently, with filtered through silica gel and the separating obtained solid of recrystallization, obtain compound 1-8 (21g, 42%).
The preparation of compound 1
5g (13.6mmol) compound 1-8 and 6.7g (19.9mmol) compound 1-5 are dissolved in the mixture that comprises 100mL toluene, 20mL ethanol and 20mL water, and add Pd (PPh
3)
41.6g (1.4mmol) with salt of wormwood 5.7g (41.2mmol).This mixture stirred 5 hours at 120 ℃, and was cooled to room temperature, with 50mL aqueous ammonium chloride solution termination reaction.Extract this mixture with 500mL EA, the organic layer that obtains cleans with 50mL distilled water.Use anhydrous MgSO
4Dry organic layer, organic solvent is removed in decompression.Subsequently, with filtered through silica gel and the separating obtained solid of recrystallization, obtain compound 1 (8.2g, 96%).
MS/FAB:623.74 (experimental value), 623.24 (theoretical values)
[preparation example 2] preparation compound 20
The preparation of compound 2-1
As the same procedure for preparing synthetic compound 1-1 among the embodiment 1 prepares compound 2-1 (13g, 83%), and difference is to use 9,9-dimethyl-9H-fluorenes-2-ylboronic acid 17.7g (74.3mmol) to replace the 1-naphthalene boronic acids.
The preparation of compound 2-2
As prepare the same procedure of synthetic compound 1-2 among the embodiment 1, use 13g (41.2mmol) compound 2-1 to prepare compound 2-2 (4.2g, 36%).
The preparation of compound 2-3
6.8g (24mmol) compound 2-2 and 1-bromo-4-iodobenzene 13.6g (48mmol) are dissolved in the 240mL toluene, and add Pd (OAc)
2270mg (1.2mmol), 50%P (i-Bu)
31.6mL (2.4mmol) and NaOt-Bu4.6g (48mmol).This mixture refluxed 2 days, and was cooled to room temperature, with 50mL saturated aqueous ammonium chloride termination reaction.Extract this mixture with 300mL EA, the organic layer that obtains cleans with 40mL distilled water.Use anhydrous MgSO
4Dry organic layer, organic solvent is removed in decompression.Subsequently, with silica gel column chromatography chromatographic separation gained solid, obtain compound 2-3 (4.3g, 41%).
The preparation of compound 2-4
As the same procedure for preparing synthetic compound 1-5 among the embodiment 1 prepares compound 2-4 (2.5g, 63%), and difference is to use 4.3g (9.8mmol) compound 2-3 to replace the 1-naphthalene boronic acids.
The preparation of compound 2-5
As the same procedure for preparing synthetic compound 1-6 among the embodiment 1 prepares compound 2-5 (16.5g, 37%), difference is to use 2,4-two chloro-quinazoline 33g (139mmol) replace 1, the 4-dibromobenzene, and use 9,9-dimethyl-9H-fluorenes-2-ylboronic acid 25g (126mmol) to replace the 1-naphthalene boronic acids.
The preparation of compound 20
As the same procedure for preparing synthetic compound 1 among the embodiment 1 prepares compound 20 (1.7g, 60%), difference is to use 1.5g (4.2mmol) compound 2-5 to replace compound 1-8, and uses 2g (5.0mmol) compound 2-4 to replace compound 1-5.
MS/FAB:679.85 (experimental value), 679.30 (calculated values)
[preparation example 3] preparation compound 23
As the same procedure for preparing synthetic compound 1 among the embodiment 1 prepares compound 23 (1.8g, 62%), and difference is to use 2g (5.0mmol) compound 2-4 to replace compound 1-5.
MS/FAB:689.84 (experimental value), 689.28 (calculated values)
[preparation example 4] preparation compound 25
The preparation of compound 4-1
As the same procedure for preparing synthetic compound 1-6 among the embodiment 1 prepares compound 4-1 (94g, 60%), difference is to use 2-naphthalene boronic acids 157g (554mmol) to replace the 1-naphthalene boronic acids, and uses 1-bromo-4-iodobenzene 100g (581.7mmol) to replace 1,4-dibromobenzene.
The preparation of compound 4-2
As the same procedure for preparing synthetic compound 1-7 among the embodiment 1 prepares compound 4-2 (57g, 67.0%), and difference is to use 94g (332mmol) compound 4-1 to replace compound 1-6.
The preparation of compound 4-3
As the same procedure for preparing synthetic compound 1-8 among the embodiment 1 prepares compound 4-3 (51g, 99.9%), and difference is to use 57g (230mmol) compound 4-2 to replace compound 1-7.
The preparation of compound 25
NaH706mg (17.6mmol) is dissolved among the 200mL DMF, and adds the compound 2-2 that is dissolved among the 200mL DMF.This mixture at room temperature stirs 1 hour, and joins lentamente among 4.3g (11.8mmol) the compound 4-3 that is dissolved in 170mLDMF.Mixture was at room temperature stirred 1 day.With 30mLMeOH and 30mL distilled water cancellation mixture, filtration under diminished pressure, and clean with distilled water and MeOH.The gained solid grinds with the order of MeOH/EA, DMF and EA/THF, is dissolved in the chloroform, filters with silicon-dioxide, and grinds with MeOH/EA, obtains compound 25 (5.5g, 76.4%).
MS/FAB:613.75 (experimental value), 613.25 (theoretical values)
[preparation example 5] preparation compound 26
The preparation of compound 5-1
100 ℃ to 30g (0.138mol) compound 1-2,1,4-dibromobenzene 98g (3 equivalent), CuI13.1g (0.5 equivalent), K
3PO
490g (3 equivalent), quadrol 9.3mL (1 equivalent) and 700mL refluxing toluene stirred 12 hours.Behind the reaction terminating, extract mixture with EA, carry out column chromatography, obtain whitening compound 5-1 (39g, 56%).
The preparation of compound 5-2
Compound 5-1 (39g), n-BuLi50.3mL (1.2 equivalent) and THF500mL stirred 30 minutes at-78 ℃.After stirring is finished, add B (OMe)
336mL (1.5 equivalent), mixture stirred 12 hours and extracted with EA.Subsequently, carry out column chromatography, obtain whitening compound 5-2 (25g, 71%).
The preparation of compound 26
6.8g (0.019mol) K of compound 2-5,9.64g (1.5 equivalent) compound 5-2,2M
3PO
4(12.4g 3 equivalent), Pd (OAC)
2(0.43g 0.1 equivalent), P (t-Bu)
33.8mL (0.3 equivalent), 120mL toluene and 60mL EtOH stirred 12 hours.After the reaction, extract mixture with EA, carry out column chromatography, obtain whitening compound 26 (5.8g, 50%).
MS/FAB:613.75 (experimental value), 613.25 (theoretical values)
[preparation example 6] preparation compound 9
The K of 6g (0.016mol) compound 1-3,8.3g (1.5 equivalent) compound 5-3,2M
2CO
3(6.8g 3 equivalent), Pd (PPh
3)
41.9g (0.1 equivalent), 100mL toluene and 50mL EtOH stirred 12 hours at 100 ℃.After the reaction, extract mixture with EA, carry out column chromatography, obtain whitening compound 9 (7g, 70%).
MS/FAB:623.74 (experimental value), 623.24 (theoretical values)
[preparation example 7] preparation compound 21
The preparation of compound 7-1
As the same procedure for preparing synthetic compound 5-2 among the embodiment 5 prepares compound 7-1 (11g, 44%), and difference is to use 11 of 15.3g (53.99mmol), 12-dihydro-12, and 12-dimethyl indeno [2,1-a] carbazole replaces compound 1-2.
The preparation of compound 7-2
As the same procedure for preparing synthetic compound 5-3 among the embodiment 5 prepares compound 7-2 (5.8g, 57%), and difference is to use 11g (0.025mmol) compound 7-1 to replace compound 5-1.
The preparation of compound 21
As the same procedure for preparing synthetic compound 26 among the embodiment 5 prepares compound 21 (3.3g, 45%), and difference is to use 5.1g (12.77mmol) compound 7-2 to replace compound 5-2.
MS/FAB:679.85 (experimental value), 679.30 (theoretical values)
[preparation example 8] preparation compound 13
The preparation of compound 8-1
As the same procedure for preparing synthetic compound 1-6 among the embodiment 1 prepares compound 8-1 (18.4g, 45%), and difference is to use 1,3-dibromobenzene 25g (0.14mol) to replace 1,4-dibromobenzene.
The preparation of compound 8-2
As the same procedure for preparing synthetic compound 1-7 among the embodiment 1 prepares compound 8-2 (10g, 63%), and difference is to use 18.4g (0.065mol) compound 8-1 to replace compound 1-6.
The preparation of compound 8-3
As the same procedure for preparing synthetic compound 1-8 among the embodiment 1 prepares compound 8-3 (4.5g, 37%), and difference is to use 8.8g (85.48mmol) compound 8-2 to replace compound 1-7.
The preparation of compound 13
As the same procedure for preparing synthetic compound 1 among the embodiment 1 prepares compound 13 (4.3g, 56%), difference is to use 4.5g (0.012mol) compound 8-3 to replace compound 1-8, and uses 4.9g (0.014mol) compound 5-2 to replace compound 1-5.
MS/FAB:623.74 (experimental value), 623.24 (theoretical values)
[preparation example 9] preparation compound 10
The preparation of compound 9-1
3-bromo-9-phenyl-9H-carbazole 50g (0.155mol) is dissolved among the THF, and slowly adds n-buLi75mL (0.186mol, 2.5M is in hexane) at-78 ℃.After one hour, add triisopropyl boric acid ester 53.5mL (0.233mol).This mixture at room temperature stirred 12 hours, and added distilled water.Extract mixture with EA, use dried over mgso, underpressure distillation with MC and hexane recrystallization, obtains compound 9-1 (33g, 0.115mol, 74%).
The preparation of compound 10
As the same procedure for preparing synthetic compound 1 among the embodiment 1 prepares compound 10 (5.7g, 9.94mmol, 73%), and difference is to use 5.87g (20.44mmol) compound 9-1 to replace compound 1-5.
MS/FAB:573.68 (experimental value), 573.22 (theoretical values)
[preparation example 10] preparation compound 14
At 120 ℃ with 5g (13.63mmol) compound 4-3,6.9g (20.45mmol) compound 5-2, Pd (PPh
3)
41.58g (1.36mmol), the K of 2M
2CO
35.65g (40.9mmol), toluene 80mL and ethanol 40mL mixed 5 hours.The mixture cool to room temperature, and add distilled water.Extract mixture with EA, underpressure distillation, and with EA and MeOH recrystallization.In addition, carry out recrystallization with THF and EA, obtain compound 14 (2.7g, 4.43mmol, 32%).
MS/FAB:623.74 (experimental value), 623.24 (theoretical values)
[preparation example 11] preparation compound 24
3.9g (10.7mmol) compound 4-3,5.2g (12.9mmol) compound 7-2 and yellow soda ash 3.4g (32.1mmol) are dissolved in the mixture that comprises 50mL toluene, 20mL ethanol and 20mL distilled water, and add Pd (PPh
3)
40.6g (0.6mmol).This mixture stirred 5 hours at 120 ℃, was cooled to room temperature, and with 300mL EA extraction, the organic layer that obtains cleans with 50mL distilled water.Use anhydrous MgSO
4Dry organic layer, organic solvent is removed in decompression.With silica gel column chromatography chromatographic separation gained solid, and recrystallization, compound 24 (2.3g, 31%) obtained.
MS/FAB:689.84 (experimental value), 689.28 (theoretical values)
[embodiment 1] uses the compound for organic electronic material of the present invention to make the OLED device
The electroluminescent material of the application of the invention is made the OLED device.At first, (15 Ω/) (available from SCP company (Samsung-Corning)) carry out ultrasonic cleaning with trieline, acetone, ethanol and distilled water to the transparency electrode ito thin film that is used for OLED successively that will be made by glass, and are stored in the Virahol before use.Then, the ITO substrate is contained in the substrate folder of vacuum vapor deposition equipment, with 4,4', 4 " three (N, N-(2-naphthyl)-phenyl amino) triphenylamine (2-TNATA) places the cell (cell) of vacuum vapor deposition equipment; then, exhaust makes indoor vacuum tightness be up to 10
-6Holder.Then, applying electric current with evaporation 2-TNATA to described cell, is the hole injection layer of 60nm thereby form thickness at the ITO substrate.Then, in another cell of vacuum vapor deposition equipment, add N, N'-two (Alpha-Naphthyl)-N, N'-phenylbenzene-4,4'-diamines (NPB) applies electric current to described cell and evaporates NPB, thereby forms the thick hole transmission layer of 20nm at described hole injection layer.After forming hole injection layer and hole transmission layer, form electroluminescence layer in the above, specific as follows.To be placed on as the compound of the present invention 1 of main body in the cell of vacuum vapor deposition equipment, will be as the Ir (piq) of doping agent
3[three (1-phenyl isoquinolin quinoline base) iridium (III)] is placed in another chamber of vacuum vapor deposition equipment.With two kinds of materials of different speed evaporation, mix with 4-10 weight % like this, thereby on hole transmission layer the thick electroluminescence layer of vapour deposition 30nm.Afterwards, three (oxine)-aluminium (III) that vapour deposition 20nm is thick on electroluminescence layer are (Alq) as electron transfer layer.Then, vapour deposition thickness be the quinolinic acid lithium (Liq) of 1-2nm as electron injecting layer, use another vacuum vapor deposition equipment to come deposit thickness to be the Al negative electrode of 150nm, thereby make the OLED device.
In the OLED device, be used as all cpds of electroluminescent material before use by 10
-6The vacuum-sublimation purifying of holder.
As a result of, electric current flows and to be 14.3mA/cm under the voltage of 6.8V
2, confirm to have launched 1050cd/m
2Ruddiness.
[embodiment 2]
Use the same procedure of embodiment 1 to make the OLED device, difference is, uses compound 18 as substrate material in electroluminescence layer.
As a result of, electric current flows and to be 15.1mA/cm under the voltage of 6.5V
2, confirm to have launched 1040cd/m
2Ruddiness.
[embodiment 3]
Use the same procedure of embodiment 1 to make the OLED device, difference is, uses compound 9 as substrate material in electroluminescence layer.
As a result of, electric current flows and to be 13.9mA/cm under the voltage of 6.5V
2, confirm to have launched 1060cd/m
2Ruddiness.
[embodiment 4]
Use the same procedure of embodiment 1 to make the OLED device, difference is, uses compound 20 as substrate material in electroluminescence layer.
As a result of, electric current flows and to be 14.5mA/cm under the voltage of 6.9V
2, confirm to have launched 1030cd/m
2Ruddiness.
[embodiment 5]
Use the same procedure of embodiment 1 to make the OLED device, difference is, uses compound 25 as substrate material in electroluminescence layer.
As a result of, electric current flows and to be 14.2mA/cm under the voltage of 7.0V
2, confirm to have launched 1050cd/m
2Ruddiness.
[comparative example 1]
Prepare the OLED device as embodiment 1 described same procedure, difference is, in electroluminescence layer, use 4,4'-two (carbazole-9-yl) biphenyl (CBP) replaces compound of the present invention as substrate material, and uses two (2-methyl-8-quinoline closes (quinolinato)) (right-phenyl-phenol) aluminium (III) (BAlq) as the hole barrier layer.
As a result of, electric current flows and to be 15.3mA/cm under the voltage of 7.5V
2, confirm to have launched 1000cd/m
2Ruddiness.
Confirmation is than traditional material, and organic electroluminescent compounds of the present invention shows excellent electroluminescent character.Use organic electroluminescent compounds of the present invention can show excellent electroluminescence characters and can reduce operating voltage as the device of substrate material, thereby increase power efficiency, and and then consumption less power.
Though described preferred implementation of the present invention for illustration purposes, it will be understood by those skilled in the art that various improvement, increase and alternative also are possible, do not deviate from the scope and spirit of the present invention that appended claims limits.
Industrial applicability
According to the present invention, the compound that is used for organic electronic material can be used for making the operating voltage with improved power efficiency and reduction, shows the OLED device of good luminous efficiency simultaneously.
Claims (10)
1. compound that is used for organic electronic material of representing with following Chemical formula 1:
Chemical formula 1
In Chemical formula 1, L
1And L
2Represent singly-bound, (C6-C30) arylidene or (C3-C30) heteroarylidene independently;
X
1And X
2Represent CR independently
4Or N, wherein X
1And X
2Not all be CR
4
Ring A represents monocycle or many ring (C6-C30) aromatic rings;
R
1To R
4Represent hydrogen independently, deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano group, (C3-C30) cycloalkyl, 5-unit to 7-unit Heterocyclylalkyl, (C2-C30) thiazolinyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxyl group, (C6-C30) aryloxy, (C3-C30) heteroaryl, (C6-C30) aryl (C1-C30) alkyl, (C6-C30) arylthio, list or two (C1-C30) alkylamino, list or two (C6-C30) arylamino, three (C1-C30) alkyl silyl, two (C1-C30) alkyl (C6-C30) aryl silyl, three (C6-C30) aryl silyl, nitro or hydroxyl;
L
1And L
2Arylidene and heteroarylidene, the aromatic ring of ring A, and R
1To R
4Alkyl, cycloalkyl, Heterocyclylalkyl, thiazolinyl, alkynyl, aryl and heteroaryl also can further be replaced by one or more substituting groups independently, and described substituting group is selected from: deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano group, (C3-C30) cycloalkyl, 5-unit to 7-unit Heterocyclylalkyl, (C2-C30) thiazolinyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxyl group, (C6-C30) aryloxy, (C3-C30) heteroaryl, (C1-C30) (C3-C30) heteroaryl of alkyl replacement, (C6-C30) (C3-C30) heteroaryl of aryl replacement, (C6-C30) aryl (C1-C30) alkyl, (C6-C30) arylthio, list or two (C1-C30) alkylamino, list or two (C6-C30) arylamino, three (C1-C30) alkyl silyl, two (C1-C30) alkyl (C6-C30) aryl silyl, (C1-C30) alkyl two (C6-C30) aryl silyl, three (C6-C30) aryl silyl, nitro and hydroxyl;
Described heteroarylidene, Heterocyclylalkyl and heteroaryl comprise one or more B of being selected from, N, O, S, P (=O), the heteroatoms of Si and P; And
Except R
2-L
2-* is the situation of hydrogen.
2. the compound tool for organic electronic material as claimed in claim 1 is characterized in that described L
1And L
2Represent singly-bound, (C6-C30) arylidene or (C3-C30) heteroarylidene independently; X
1And X
2Represent CR independently
4Or N, wherein X
1And X
2Not all be CR
4Ring A represents monocycle or many ring (C6-C30) aromatic rings; R
1To R
4Represent hydrogen, deuterium, (C6-C30) aryl or (C3-C30) heteroaryl independently; L
1And L
2Arylidene and heteroarylidene, the ring A aromatic ring and R
1To R
4Aryl and heteroaryl one or more substituting groups that can be independently be selected from down group further replace: (C3-C30) heteroaryl that (C3-C30) heteroaryl that deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, (C6-C30) aryl, (C3-C30) heteroaryl, (C1-C30) alkyl replace, (C6-C30) aryl replace and (C6-C30) aryl (C1-C30) alkyl.
3. the compound for organic electronic material as claimed in claim 2 is characterized in that:
R
aAnd R
bExpression (C1-C7) alkyl or (C6-C12) aryl independently;
R
cTo R
eRepresent (C3-C30) heteroaryl that hydrogen, deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, (C6-C30) aryl, (C3-C30) heteroaryl, (C1-C30) alkyl replaces, (C3-C30) heteroaryl that (C6-C30) aryl replaces and (C6-C30) aryl (C1-C30) alkyl independently;
R
1-L
1-* and R
2-L
2-* represents hydrogen independently or is selected from following structure, except R
2-L
2-* is the situation of hydrogen:
4. the compound for organic electronic material as claimed in claim 3 is characterized in that, described compound is selected from following compound:
5. organic electroluminescence device, it comprises each described compound for organic electronic material among the claim 1-4.
6. organic electroluminescence device as claimed in claim 5 is characterized in that, described device comprises first electrode; Second electrode; And inserting one or more layers organic layer between described first electrode and second electrode, wherein said organic layer comprises one or more compound and one or more phosphorescent dopants of being used for organic electronic material.
7. organic electroluminescence device as claimed in claim 6 is characterized in that, described organic layer also comprises one or more amine compound that are selected from aromatic amine compound and styryl aromatic amine compound.
8. organic electroluminescence device as claimed in claim 6, it is characterized in that described organic layer also comprises one or more metals or its title complex of organo-metallic, period 4 and the period 5 transition metal, lanthanide series metal and the d-transition element that are selected from the 1st family in the periodic table of elements, the 2nd family.
9. organic electroluminescence device as claimed in claim 6 is characterized in that, described organic layer comprises electroluminescence layer and charge generation layer.
10. organic electroluminescence device as claimed in claim 6 is characterized in that, described organic layer also comprises the organic electro luminescent layer of one or more layers red-emitting, green glow and blue light, with the emission white light.
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| KR1020100099585A KR20120038060A (en) | 2010-10-13 | 2010-10-13 | Novel compounds for organic electronic material and organic electroluminescent device using the same |
| KR10-2010-0099585 | 2010-10-13 | ||
| PCT/KR2011/007544 WO2012050347A1 (en) | 2010-10-13 | 2011-10-11 | Novel compounds for organic electronic material and organic electroluminescent device using the same |
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| CN2011800586027A Pending CN103249800A (en) | 2010-10-13 | 2011-10-11 | Novel compounds for organic electronic material and organic electroluminescent device using the same |
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| JP (1) | JP2013546171A (en) |
| KR (1) | KR20120038060A (en) |
| CN (1) | CN103249800A (en) |
| TW (1) | TW201226398A (en) |
| WO (1) | WO2012050347A1 (en) |
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| CN110305057A (en) * | 2019-04-27 | 2019-10-08 | 安徽秀朗新材料科技有限公司 | A kind of preparation method of bromo- 7H- benzo [c] carbazole of 10- |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012050347A1 (en) | 2012-04-19 |
| JP2013546171A (en) | 2013-12-26 |
| TW201226398A (en) | 2012-07-01 |
| KR20120038060A (en) | 2012-04-23 |
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