CN101414662B - Organic electronic transmission and/or positive hole countercheck material, and synthesizing method and purpose thereof - Google Patents

Organic electronic transmission and/or positive hole countercheck material, and synthesizing method and purpose thereof Download PDF

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CN101414662B
CN101414662B CN 200710176009 CN200710176009A CN101414662B CN 101414662 B CN101414662 B CN 101414662B CN 200710176009 CN200710176009 CN 200710176009 CN 200710176009 A CN200710176009 A CN 200710176009A CN 101414662 B CN101414662 B CN 101414662B
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phenanthrene
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CN101414662A (en
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汪鹏飞
李娜
刘卫敏
李述汤
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention belongs to the field of organic electron transmission/hole blocking organic materials for organic electroluminescent devices, and particularly relates to a polyaryl-substituted pyridine derivative used in the organic electron transmission materials and/or the organic hole blocking organic materials, a synthetic method as well as the usage of the polyaryl-substituted pyridine derivative material for preparing an organic electroluminescent device. By a molecular design, a plurality of large substituents with rigid structures are introduced, which causes an exciplex not to easily form in the derivative, inhibits the crystallization course thereof, improves the film forming thereof and improves the charge transfer property thereof; meanwhile, the breakage of the molecular coplanarity causes a blue shift of the emission peak of the derivative, thus achieving the purpose of improving the performance of the device. The polyaryl-substituted pyridine derivative comprises the structure.

Description

Organic electronic transmission and/or hole barrier materials and preparation method and use thereof
Technical field
The invention belongs to the organic electronic transmission/hole barrier materials field in the organic electroluminescence device, be particularly related to a class polyaryl substituted pyridine derivative and a synthetic method thereof that is used for organic electronic transmission and/or hole barrier materials, and with the purposes of such polyaryl substituted pyridine derivative material preparation organic electroluminescence device aspect.
Background technology
Along with the arriving of Development of Multimedia Technology and information-intensive society, more and more higher to the flat-panel monitor performance demands.In recent years emerging three kinds of Display Techniques: plasma display, Field Emission Display and display of organic electroluminescence (OLED) have all remedied the deficiency of cathode ray tube (CRT) and LCD (LCD) to a certain extent.Wherein, a series of advantages such as OLED has from main light emission, low-voltage DC driven, solidifies entirely, the visual angle is wide, color is abundant, compare with LCD, OLED does not need backlight, the visual angle is big, low in energy consumption, its response speed reaches 1000 times of LCD, its manufacturing cost but is lower than the LCD of equal resolution, therefore, organic electroluminescent LED (OLEDs) is owing to its potential application in display of new generation and lighting technology causes extensive attention, and its application prospect is very wide.Organic electroluminescence device is spontaneous luminescent device, and the luminous mechanism of OLED is under the extra electric field effect, and electronics and hole are injected the back from positive and negative polarities respectively and produced luminous in organic material migration, compound and decay.The typical structure of OLED comprises cathode layer, anode layer, and the organic thin film layer between this is two-layer, can comprise one or more functional layers in electron injecting layer, electron transfer layer, hole blocking layer, hole transmission layer, hole injection layer and the organic luminous layer in the organic thin film layer.Since the C.W.Tang of Eastman Kodak Company (C.W.Tang and S.A.Vans lyke, Applied Physics Letters, Volume 51, P913,1987) reported since the laminated type organic electroluminescent device of low voltage drive, people have carried out a lot of researchs (U.S.Pat.Nos.5,141,671 to utilizing organic material as the organic electroluminescence device of composition material; 4,539,507; 6,020,078; 5,935,720; 5,972,247; 5,593,788; 4,885,211; 5,059,862; 5,104,740; 5,069,975; 5,126,214; 5,389,444; 6,165,383; 6,245,449; 6,861,162 B2; 6,833,202 B2; Chen, Shi and Tang, Macromol.Symp., 1997,125,1; Segura, Acta.Polym., 1998,49,319; Mitschke and Bauerle, J.Mater.Chem.2000,10,1471).Yet, although the progress of organic electroluminescent is very fast, but still have a lot of problems to be badly in need of solving, as the raising of external quantum efficiency (EQE), the design of the design of the new material that colorimetric purity is higher and synthetic, efficent electronic transmission/hole barrier new material with synthesize etc.For organic electroluminescence device, the luminous quantum efficiency of device is the concentrated expression of various factors, also is an important indicator weighing device quality.In general, causing a low main cause of device EQE, is to be injected with transmission is uneven by the electric charge of luminescent material to cause.Simultaneously, this imbalance also seriously influences the stability of device, makes device not reach the requirement of practicability.If can not reach balance, then electric current will be done invalid (not luminous) and flow.For example, if we can not make the zone (normally luminescent layer) of compound local some hope in device of charge carrier, and make it to betide the electrode of easy quencher and operation material at the interface, then the luminous quantum efficiency of device will reduce greatly.Overcoming this difficulty must make the potential barrier at two electrodes and operation material boundary layer place that a kind of rational arrangement is arranged.The generation of potential barrier is to cause because of just there are differences between (or negative) work function of electrode and the ionization potential of operation material (or electron affinity energy), can under lower driving voltage, carry out for the injection that will guarantee charge carrier, require these potential barriers can not be too high in general.For this reason, must do certain prediction to the height of potential barrier.But regrettably the ionization potential (IP) or the electron affinity energy (EA) of relevant these operation materials are reported very few in the literature, and generally relatively disperse by the numerical value that Theoretical Calculation obtains, this just is difficult to select suitable electric transmission/hole barrier new material to make it to be complementary with electrode material.Because a lot of organic materials are transporting holes effectively, so, under many circumstances, often additionally add one deck electric transmission/hole blocking layer in negative electrode one side in order to improve the luminous efficiency of device, with the blocking hole transmission, with the compound luminescent layer zone that is limited in of charge carrier.2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolene (BCP) and 1,3,5-three (N-phenyl-2-benzimidazole) benzene (TPBI) is the electric transmission/hole barrier materials that is widely used in the electroluminescent device, but its stability in device remains further to be improved.Other hole barrier materials be two (2-methyl-oxine) (4 one phenylol) aluminium ((II1) (BAIq).The life-span of its device and stability can both significantly improve, and contain the luminous efficiency low significantly (about 40%) of BCP (T.Watanabe et al., Proc.SPIE 2001,4105,175) device but shortcoming is the luminous efficiency ratio that contains the BAlq device.Therefore, although BAlq can realize the good life-span, generally speaking not gratifying hole barrier materials, its reason is that prepared device efficiency is too low.
Pyridine ring is because its short of electricity sub-feature has certain electronegativity, and its reduction potential is about 2.6eV (vsSCE).Its polymer, at 2.9～3.5eV, and therefore Ip can be used as the electron transport material in the polymer electroluminescent device at 5.7～6.3eV as the EA value of polypyridine.Yet,, its luminosity is changed because its strong intramolecular interaction (overlapping as ∏-∏) easily forms exciplex in film.Therefore, device performance is not good enough.So far seldom in organic electroluminescence device, use.
Summary of the invention
The objective of the invention is to overcome the problem that exists in the above-mentioned organic electronic transmission/hole barrier materials, the organic electronic transmission and/or the hole barrier materials of a class polyaryl substituted pyridine derivative is provided; By MOLECULE DESIGN, introduce some large-substituents and make it be difficult for forming exciplex, and suppress its crystallization process with rigid structure, improve its film forming, improve its charge transport properties; Simultaneously, the destruction of molecule coplanarity will make its emission peak blue shift, and then reach the purpose of improving device performance.
A further object of the present invention provides the organic electronic transmission of purpose one and/or the synthetic method of hole sun obstructing material.
Organic electronic transmission and/or hole barrier materials that an also purpose of the present invention provides purpose one are used to prepare organic electroluminescence device, especially the purposes of blue organic electroluminescence device aspect.
The present invention relates to the organic electronic transmission and/or the hole barrier materials of the polyaryl substituted pyridine derivative of a class tool electrophilic character, this compounds has very high electron affinity (about 3.5eV) and ionization potential (about 7.0eV), can be used for the electron transport material and/or the hole barrier materials of organic electroluminescence device.The molecular structure of material of the present invention is shown in following general formula.With the prepared organic electroluminescence device of material of the present invention because and have only very little barrier potential (about 0.2eV) between the negative electrode, electronic energy is injected in the organic luminous layer effectively, so its device has a very low bright voltage (2.7eV), simultaneously because high ionization potential (about 7.0eV) is arranged, blocking hole is diffused into negative electrode effectively, thereby the limit that reaches hole and electronics obtains effect.Material of the present invention has very high photoluminescence efficiency (about 100%) and ultra-violet (UV) band emission wavelength (370nm), there is not the quencher phenomenon that causes because of power conversion, can be used for making all organic electroluminescence devices, blue-light device particularly, thus the performance of corresponding electron luminescence device improved effectively.Material of the present invention has high glass-transition temperature and high thermal stability simultaneously, so the life-span of electroluminescent device is effectively improved.
The present invention adopts easy method to synthesize a series of class polyaryl substituted pyridine derivatives with efficent electronic transmission and/or hole barrier materials.Organic electroluminescence device of the present invention comprises negative electrode, anode and organic thin film layer, at least comprise organic luminous layer in the organic thin film layer between negative electrode and anode, and in the organic thin film layer at least one deck comprise following general formula (I), (II) or (III) the polyaryl substituted pyridine derivative of expression.The polyaryl substituted pyridine derivative that preferred organic thin film layer comprises general formula (I), (II) or (III) represents.The molecular structure of a class polyaryl substituted pyridine derivative of the present invention is as follows:
Figure S2007101760098D00041
Wherein:
R 1, R 3, R 3', R 4, R 4' substituting group can be identical or different, independently be selected from hydrogen respectively, have the replacement or the unsubstituted alkyl of 1 to 20 carbon atom, replacement or unsubstituted cycloalkyl with 5 to 20 carbon atoms, have 1 to 20 carbon atom alkoxyl, have 6 to 60 carbon atoms aralkyl, have 6 to 50 ring carbon atoms aryl, have the aryloxy group of 6 to 50 annular atomses or have a kind of in the aromatic heterocyclic group of 5 to 50 annular atomses;
R 2, R 2', R 5, R 5' substituting group can be identical or different, independently be selected from hydrogen, carboxyl, fluoro methyl, cyano group, nitro respectively or have a kind of in the ester group etc. of 2 to 20 carbon atoms;
Ar 1, Ar 1', Ar 2, Ar 2' substituting group can be identical or different, independently be selected from aryl respectively or have a kind of in the aromatic heterocyclic group of 5 to 50 annular atomses with 6 to 50 ring carbon atoms.
Described R 1, R 3, R 3', R 4, R 4' in the not substituted alkyl with 1 to 20 carbon atom be methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl or n-octyl.
Described R 1, R 3, R 3', R 4, R 4' in the substituted alkyl with 1 to 20 carbon atom be methylol, the 1-ethoxy, the 2-ethoxy, 2-hydroxyl isobutyl group, 1, the 2-dihydroxy ethyl, 1,3-dihydroxy isopropyl, 2, the 3 one dihydroxy-tert-butyl group, 1,2,3 one trihydroxy propyl group, chloromethyl, the 1-chloroethyl, the 2-chloroethyl, 2-chlorine isobutyl group, 1, the 2-Dichloroethyl, 1,3-two chloro isopropyls, 2, the 3-two chloro-tert-butyl groups, 1,2,3-three chloropropyls, bromomethyl, the 1-bromoethyl, the 2-bromoethyl, 2-melts isobutyl group, 1,2-two bromoethyls, 1,3-dibromo isopropyl, 2, the 3-two bromo-tert-butyl groups, 1,2,3-three bromopropyls, iodomethyl, 1-iodine ethyl, 2-iodine ethyl, 2-iodine isobutyl group, 1,2-diiodo-ethyl, 1,3-diiodo-isopropyl, 2, the 3-two iodo-tert-butyl groups, 1,2,3-triiodo propyl group, amino methyl, the 1-amino-ethyl, the 2-amino-ethyl, 2-aminoisobutyric base, 1, the 2-diamino ethyl, 1,3-diaminourea isopropyl, 2,3-diaminourea-tert-butyl group or 1,2,3-triamido propyl group.
Described R 1, R 3, R 3', R 4, R 4' in the unsubstituted cycloalkyl with 5 to 20 carbon atoms be cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl.
Described R 1, R 3, R 3', R 4, R 4' in the cycloalkyl of replacement with 5 to 20 carbon atoms be 4-methylcyclohexyl, adamantyl or norborneol alkyl.
Described R 1, R 3, R 3', R 4, R 4' in the alkoxyl with 1 to 20 carbon atom be by-group that OR represents.Wherein the group represented of R is an alkyl, alkyl comprises methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, methylol, the 1-ethoxy, the 2-ethoxy, 2-hydroxyl isobutyl group, 1, the 2-dihydroxy ethyl, 1,3-two chloro isopropyls, 2, the 3-two chloro-tert-butyl groups, 1,2,3-three chloropropyls, bromomethyl, the 1-bromoethyl, the 2-bromoethyl, 2-bromine isobutyl group, 1,2-two bromoethyls, 1,3-dibromo isopropyl, 2, the 3-two bromo-tert-butyl groups, 1,2,3-three bromopropyls, iodomethyl, 1-iodine ethyl, 2-iodine ethyl, 2-iodine isobutyl iodide 1,2-diiodo-ethyl, 1,3-diiodo-isopropyl, 2, the 3-two iodos-tert-butyl group, 1,2,3-triiodo propyl group, iodomethyl, 1-iodine ethyl, 2-iodine ethyl, 2-iodine isobutyl group, 1,2-diiodo-ethyl, 1,3-diiodo-isopropyl, 2, the 3-two iodo-tert-butyl groups, 1,2,3-triiodo propyl group, amino methyl, the 1-amino-ethyl, the 2-amino-ethyl, 2-aminoisobutyric base, 1, the 2-diamino ethyl, 1,3-diaminourea isopropyl, 2,3-diaminourea-tert-butyl group, 1,2,3-triamido propyl group, cyano methyl, the 1-cyano ethyl, the 2-cyano ethyl, 2-cyano group isobutyl group, 1,2-dicyano ethyl, 1,3-dicyano isopropyl, 2,3-dicyano-tert-butyl group, 1,2,3-tricyano propyl group, the nitro methyl, the 1-nitro-ethyl, the 2-nitro-ethyl, 2-nitro isobutyl group, 1,2-dinitro ethyl, 1,3-dinitro isopropyl, 2,3-dinitro-tert-butyl group or 1,2,3-trinitro-propyl group.
Described R 1, R 3, R 3', R 4, R 4' in have 6 to 60 carbon atoms aralkyl be benzyl, 1-phenylethyl, the 2-phenylethyl, 1-propyloxy phenyl base, 2-propyloxy phenyl base, the phenyl tert-butyl group, the Alpha-Naphthyl methyl, 1-Alpha-Naphthyl ethyl, 2-Alpha-Naphthyl ethyl, 1-Alpha-Naphthyl isopropyl, 2-Alpha-Naphthyl isopropyl, the betanaphthyl methyl, 1-betanaphthyl ethyl, 2-betanaphthyl ethyl, 1-betanaphthyl isopropyl, 2-betanaphthyl isopropyl, 1-pyrrole radicals methyl, 2-(1-pyrrole radicals) ethyl, to methyl-benzyl, between methyl-benzyl, adjacent methyl-benzyl, p-chlorobenzyl, the m-chloro benzyl, o-chlorobenzyl, to bromobenzyl, between bromobenzyl, adjacent bromobenzyl, to the iodine benzyl, between the iodine benzyl, adjacent iodine benzyl, PAB, between aminobenzyl, adjacent aminobenzyl, to nitrobenzyl, between nitrobenzyl, adjacent nitrobenzyl, to the cyano group benzyl, between the cyano group benzyl, o-cyanobenzyl, 1-chloro-2-propyloxy phenyl base or trityl.
Described R 1, R 3, R 3', R 4, R 4' in have 6 to 50 ring carbon atoms aryl be phenyl, the 1-naphthyl, the 2-naphthyl, the 1-anthryl, the 2-anthryl, the 9-anthryl, the 1-phenanthryl, the 2-phenanthryl, the 3-phenanthryl, the 4-phenanthryl, the 9-phenanthryl, 1-aphthacene base, 2-aphthacene base, 9-aphthacene base, the 1-pyrenyl, the 2-pyrenyl, the 4-pyrenyl, the 2-xenyl, the 3-xenyl, the 4-xenyl, para-terpheny-4-base, para-terpheny-3-base, para-terpheny-2-base, meta-terphenyl-4-base, meta-terphenyl-3-base, meta-terphenyl-2-base, o-tolyl, between tolyl, p-methylphenyl, to tert-butyl-phenyl, right-(2-phenyl propyl) phenyl, 3-methyl-2-naphthyl, 4-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-anthryl, 4 '-methyl biphenyl or 4 "-tert-butyl group-para-terpheny-4-base.
Described R 1, R 3, R 3', R 4, R 4' in have 6 to 50 annular atomses aryloxy group be by-group that OAr represents.Wherein the group represented of Ar is an aromatic group, aromatic group comprises phenyl, the 1-naphthyl, the 2-naphthyl, the 1-anthryl, the 2-anthryl, the 9-anthryl, the 1-phenanthryl, the 2-phenanthryl, the 3-phenanthryl, the 4-phenanthryl, the 9-phenanthryl, 1-aphthacene base, 2-aphthacene base, 9-aphthacene base, the 1-pyrenyl, the 2-pyrenyl, the 4-pyrenyl, the 2-xenyl, the 3-xenyl, the 4-xenyl, para-terpheny-4-base, para-terpheny-3-base, para-terpheny-2-base, meta-terphenyl-4-base, meta-terphenyl-3-base, meta-terphenyl-2-base, o-tolyl, between tolyl, p-methylphenyl, to tert-butyl-phenyl, right-(2-phenyl propyl) phenyl, 3-methyl-2-naphthyl, 4-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-naphthyl, 4 '-methyl biphenyl; 4 "-the tert-butyl group-para-terpheny-4-base, the 2-pyrrole radicals, the 3-pyrrole radicals, pyridine radicals, the 2-pyridine radicals, the 3-pyridine radicals, the 4-pyridine radicals, the 2-indyl, the 3-indyl, the 4-indyl, the 5-indyl, the 6-indyl, the 7-indyl, the 1-isoindolyl, the 3-isoindolyl, the 4-isoindolyl, the 5-isoindolyl, the 6-isoindolyl, the 7-isoindolyl, the 2-furyl, the 3-furyl, the 2-benzofuranyl, the 3-benzofuranyl, the 4-benzofuranyl, the 5-benzofuranyl, the 6-benzofuranyl, the 7-benzofuranyl, the 1-isobenzofuran-base, the 3-isobenzofuran-base, the 4-isobenzofuran-base, the 5-isobenzofuran-base, the 6-isobenzofuran-base, 7-isobenzofuran-base 2-quinolyl, the 3-quinolyl, the 4-quinolyl, the 5-quinolyl, the 6-quinolyl, the 7-quinolyl, the 8-quinolyl, the 1-isoquinolyl, the 3-isoquinolyl, the 4-isoquinolyl, the 5-isoquinolyl, the 6-isoquinolyl, the 7-isoquinolyl, the 8-isoquinolyl, the 2-quinoxalinyl, the 5-quinoxalinyl, the 6-quinoxalinyl, the 1-carbazyl, the 2-carbazyl, the 3-carbazyl, the 4-carbazyl, the 1-phenanthridinyl, the 2-phenanthridinyl, the 3-phenanthridinyl, the 4-phenanthridinyl, the 6-phenanthridinyl, the 7-phenanthridinyl, the 8-phenanthridinyl, the 9-phenanthridinyl, the 10-phenanthridinyl, the 1-acridinyl, the 2-acridinyl, the 3-acridinyl, the 4-acridinyl, the 9-acridinyl, 1, the 7-phenanthrene is coughed up beautiful jade-2-base, 1, the 7-phenanthrene is coughed up beautiful jade-3-base, 1, the 7-phenanthrene is coughed up beautiful jade-4-base, 1, the 7-phenanthrene is coughed up beautiful jade-5-base, 1, the 7-phenanthrene is coughed up beautiful jade-6-base, 1, the 7-phenanthrene is coughed up beautiful jade-8-base, 1, the 7-phenanthrene is coughed up beautiful jade-9-base, 1, the 7-phenanthrene is coughed up beautiful jade-10-base, 1, the 8-phenanthrene is coughed up beautiful jade-2-base, 1, the 8-phenanthrene is coughed up beautiful jade-3-base, 1, the 8-phenanthrene is coughed up beautiful jade-4-base, 1, the 8-phenanthrene is coughed up beautiful jade-5-base, 1, the 8-phenanthrene is coughed up beautiful jade-6-base, 1, the 8-phenanthrene is coughed up beautiful jade-7-base, 1, the 8-phenanthrene is coughed up beautiful jade-9-base, 1, the 8-phenanthrene is coughed up beautiful jade-10-base, 1, the 9-phenanthrene is coughed up beautiful jade-2-base, 1, the 9-phenanthrene is coughed up beautiful jade-3-base, 1, the 9-phenanthrene is coughed up beautiful jade-4-base, 1, the 9-phenanthrene is coughed up beautiful jade-5-base, 1, the 9-phenanthrene is coughed up beautiful jade-6-base, 1, the 9-phenanthrene is coughed up beautiful jade-7-base, 1, the 9-phenanthrene is coughed up beautiful jade-8-base, 1, the 9-phenanthrene is coughed up beautiful jade-10-base, 1, the 10-phenanthrene is coughed up beautiful jade-2-base, 1, the 10-phenanthrene is coughed up beautiful jade-3-base, 1, the 10-phenanthrene is coughed up beautiful jade-4-base, 1, the 10-phenanthrene is coughed up beautiful jade-5-base, 2, the 9-phenanthrene is coughed up beautiful jade-1-base, 2, the 9-phenanthrene is coughed up beautiful jade-3-base, 2, the 9-phenanthrene is coughed up beautiful jade-4-base, 2, the 9-phenanthrene is coughed up beautiful jade-5-base, 2, the 9-phenanthrene is coughed up beautiful jade-6-base, 2, the 9-phenanthrene is coughed up beautiful jade-7-base, 2, the 9-phenanthrene is coughed up beautiful jade _ 8-base, 2, the 9-phenanthrene is coughed up beautiful jade-10-base, 2, the 8-phenanthrene is coughed up beautiful jade-1-base, 2, the 8-phenanthrene is coughed up beautiful jade-3-base, 2, the 8-phenanthrene is coughed up beautiful jade-4-base, 2, the 8-phenanthrene is coughed up beautiful jade-5-base, 2, the 8-phenanthrene is coughed up beautiful jade-6-base, 2, the 8-phenanthrene is coughed up beautiful jade-7-base, 2, the 8-phenanthrene is coughed up beautiful jade-9-base, 2, the 8-phenanthrene is coughed up beautiful jade-10-base, 2, the 7-phenanthrene is coughed up beautiful jade-1-base, 2, the 7-phenanthrene is coughed up beautiful jade-3-base, 2, the 7-phenanthrene is coughed up beautiful jade-4-base, 2, the 7-phenanthrene is coughed up beautiful jade-5-base, 2, the 7-phenanthrene is coughed up beautiful jade-6-base, 2, the 7-phenanthrene is coughed up beautiful jade-8-base, 2, the 7-phenanthrene is coughed up beautiful jade-9-base, 2, the 7-phenanthrene is coughed up beautiful jade-10-base, the 1-phenazinyl, the 2-phenazinyl, the 1-phenothiazinyl, the 2-phenothiazinyl, the 3-phenothiazinyl, the 4-phenothiazinyl, the 1-phenoxazine group, the 2-phenoxazine group, the 3-phenoxazine group, the 4-phenoxazine group, the 2-oxazole. base, the 4-oxazolyl, the 5-oxazolyl, 2-oxadiazole base, 5-oxadiazole base, 3-furazan base, the 2-thienyl, the 3-thienyl, 2-methylpyrrole-1-base, 2-methylpyrrole-3-base, 2-methylpyrrole-4-base, 2-methylpyrrole-5-base, 3-methylpyrrole-1-base, 3-methylpyrrole-2-base, 3-methylpyrrole-4-base, 3-methylpyrrole-5-base, 2-tert-butyl group pyrroles-4-base, 3-(2-phenyl propyl) pyrroles-1-base, 2-methyl isophthalic acid-indyl, 4-methyl isophthalic acid-indyl, 2-methyl-3-indyl, 4-methyl-3-indyl, the 2-tert-butyl group-1-indyl, the 4-tert-butyl group-1-indyl, the 2-tert-butyl group-3-indyl or the 4-tert-butyl group-3-indyl.
Described R 1, R 3, R 3', R 4, R 4' in have 5 to 50 annular atomses aromatic heterocyclic group be the 1-pyrrole radicals, the 2-pyrrole radicals, the 3-pyrrole radicals, pyridine radicals, the 2-pyridine radicals, the 3-pyridine radicals, the 4-pyridine radicals, the 1-indyl, the 2-indyl, the 3-indyl, the 4-indyl, the 5-indyl, the 6-indyl, the 7-indyl, the 1-isoindolyl, the 2-isoindolyl, the 3-isoindolyl, the 4-isoindolyl, the 5-isoindolyl, the 6-isoindolyl, the 7-isoindolyl, the 2-furyl, the 3-furyl, the 2-benzofuranyl, the 3-benzofuranyl, the 4-benzofuranyl, the 5-benzofuranyl, the 6-benzofuranyl, the 7-benzofuranyl, the 1-isobenzofuran-base, the 3-isobenzofuran-base, the 4-isobenzofuran-base, the 5-isobenzofuran-base, the 6-isobenzofuran-base, the 7-isobenzofuran-base, the 2-quinolyl, the 3-quinolyl, the 4-quinolyl, the 5-quinolyl, the 6-quinolyl, the 7-quinolyl, the 8-quinolyl, the 1-isoquinolyl, the 3-isoquinolyl, the 4-isoquinolyl, the 5-isoquinolyl, the 6-isoquinolyl, the 7-isoquinolyl, the 8-isoquinolyl, 2-quinoxalinyl (quinoxanyl), 5-quinoxalinyl (quinoxanyl), 6-quinoxalinyl (quinoxanyl), the 1-carbazyl, the 2-carbazyl, the 3-carbazyl, the 4-carbazyl, the 9-carbazyl, 1-coffee pyridine base, 2-coffee pyridine base, 3-coffee pyridine base, 4-coffee pyridine base, 6-coffee pyridine base, 7-coffee pyridine base, 8-coffee pyridine base, 9-coffee pyridine base, 10-coffee pyridine base, the 1-acridinyl, the 2-acridinyl, the 3-acridinyl, the 4-acridinyl, the 9-acridinyl, 1, the 7-phenanthrene is coughed up beautiful jade-2-base, 1, the 7-phenanthrene is coughed up beautiful jade-3-base, 1, the 7-phenanthrene is coughed up beautiful jade-4-base, 1, the 7-phenanthrene is coughed up beautiful jade-5-base, 1, the 7-phenanthrene is coughed up beautiful jade-6-base, 1, the 7-phenanthrene is coughed up beautiful jade-8-base, 1, the 7-phenanthrene is coughed up beautiful jade-9-base, 1, the 7-phenanthrene is coughed up beautiful jade-10-base, 1, the 8-phenanthrene is coughed up beautiful jade-2-base, 1, the 8-phenanthrene is coughed up beautiful jade-3-base, 1, the 8-phenanthrene is coughed up beautiful jade-4-base, 1, the 8-phenanthrene is coughed up beautiful jade-5-base, 1, the 8-phenanthrene is coughed up beautiful jade-6-base, 1, the 8-phenanthrene is coughed up beautiful jade-7-base, 1, the 8-phenanthrene is coughed up beautiful jade-9-base, 1, the 8-phenanthrene is coughed up beautiful jade-10-base, 1, the 9-phenanthrene is coughed up beautiful jade-2-base, 1, the 9-phenanthrene is coughed up beautiful jade-3-base, 1, the 9-phenanthrene is coughed up beautiful jade-4-base, 1, the 9-phenanthrene is coughed up beautiful jade-5-base, 1, the 9-phenanthrene is coughed up beautiful jade-6-base, 1, the 9-phenanthrene is coughed up beautiful jade-7-base, 1, the 9-phenanthrene is coughed up beautiful jade-8-base, 1, the 9-phenanthrene is coughed up beautiful jade-10-base, 1, the 10-phenanthrene is coughed up beautiful jade-2-base, 1, the 10-phenanthrene is coughed up beautiful jade-3-base, 1, the 10-phenanthrene is coughed up beautiful jade-4-base, 1, the 10-phenanthrene is coughed up beautiful jade-5-base, 2,9-phenanthrolines-1-base, 2, the 9-phenanthrene is coughed up beautiful jade-3-base, 2, the 9-phenanthrene is coughed up beautiful jade-4-base, 2, the 9-phenanthrene is coughed up beautiful jade-5-base, 2, the 9-phenanthrene is coughed up beautiful jade-6-base, 2, the 9-phenanthrene is coughed up beautiful jade-7-base, 2, the 9-phenanthrene is coughed up beautiful jade-8-base, 2, the 9-phenanthrene is coughed up beautiful jade-10-base, 2, the 8-phenanthrene is coughed up beautiful jade-1-base, 2, the 8-phenanthrene is coughed up beautiful jade-3-base, 2, the 8-phenanthrene is coughed up beautiful jade-4-base, 2, the 8-phenanthrene is coughed up beautiful jade-5-base, 2, the 8-phenanthrene is coughed up beautiful jade-6-base, 2, the 8-phenanthrene is coughed up beautiful jade-7-base, 2, the 8-phenanthrene is coughed up beautiful jade-9-base, 2, the 8-phenanthrene is coughed up beautiful jade-10-base, 2, the 7-phenanthrene is coughed up beautiful jade-1-base, 2, the 7-phenanthrene is coughed up beautiful jade-3-base, 2, the 7-phenanthrene is coughed up beautiful jade-4-base, 2, the 7-phenanthrene is coughed up beautiful jade-5-base, 2, the 7-phenanthrene is coughed up beautiful jade-6-base, 2, the 7-phenanthrene is coughed up beautiful jade-8-base, 2, the 7-phenanthrene is coughed up beautiful jade-9-base, 2, the 7-phenanthrene is coughed up beautiful jade-10-base, the 1-phenazinyl, the 2-phenazinyl, the 1-phenothiazinyl, the 2-phenothiazinyl, the 3-phenothiazinyl, the 4-phenothiazinyl, the lysivane base, the 1-phenoxazine group, the 2-phenoxazine group, the 3-phenoxazine group, the 4-phenoxazine group, the 10-phenoxazine group, the 2-oxazolyl, the 4-oxazolyl, the 5-oxazolyl, 2-oxadiazole base, 5-oxadiazole base, 3-furazan base (furazanyl), the 2-thienyl, the 3-thienyl, 2-picoline-1-base, 2-methylpyrrole-3-base, 2-methylpyrrole-4-base, 2-methylpyrrole-5-base, 3-methylpyrrole-1-base, 3-methylpyrrole-2-base, 3-methylpyrrole-4-base, 3-methylpyrrole-5-base, 2-tert-butyl group pyrroles-4-base, 3-(2-phenyl propyl) pyrroles one-1-base, 2-methyl isophthalic acid-indyl, 4-methyl isophthalic acid-indyl, 2-methyl-3-indyl, 4-methyl-3-indyl, the 2-tert-butyl group-1-indyl, the 4-tert-butyl group-1-indyl, the 2-tert-butyl group-3-indyl or the 4-tert-butyl group-3-indyl.
Described R 2, R 2', R 5, R 5' in the fluoro methyl be the methyl that a fluorine (as the 1-methyl fluoride), difluoro (as 1, the 1-difluoromethyl) or trifluoro (as 1,1, the 1-trifluoromethyl) replace.
Described R 2, R 2', R 5, R 5' in have 2 to 20 carbon atoms ester group be carbomethoxy, ethoxycarbonyl, propyl ester base, isopropyl ester base, positive butyl ester base, Zhong Ding ester group, isobutyl ester group, n-pentyl ester base, just own ester group, positive heptyl ester base or n-octyl base.
Described Ar 1, Ar 1', Ar 2, Ar 2' in have 6 to 50 ring carbon atoms aryl be phenyl, the 1-naphthyl, the 2-naphthyl, the 1-anthryl, the 2-anthryl, the 9-anthryl, the 1-phenanthryl, the 2-phenanthryl, the 3-phenanthryl, the 4-phenanthryl, the 9-phenanthryl, 1-aphthacene base, 2-aphthacene base, 9-aphthacene base, the 1-pyrenyl, the 2-pyrenyl, the 4-pyrenyl, the 2-xenyl, the 3-xenyl, the 4-xenyl, para-terpheny-4-base, para-terpheny-3-base, para-terpheny-2-base, meta-terphenyl-4-base, meta-terphenyl-3-base, meta-terphenyl-2-base, o-tolyl, between tolyl, p-methylphenyl, to tert-butyl-phenyl, right-(2-phenyl propyl) phenyl, 3-methyl-2-naphthyl, 4-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-anthryl, 4 '-methyl biphenyl or 4 "-tert-butyl group-para-terpheny-4-base.
Described Ar 1, Ar 1', Ar 2, Ar 2' in have 5 to 50 annular atomses aromatic heterocyclic radical be the 1-pyrrole radicals, the 2-pyrrole radicals, the 3-pyrrole radicals, pyridine radicals, the 2-pyridine radicals, the 3-pyridine radicals, the 4-pyridine radicals, the 1-indyl, the 2-indyl, the 3-indyl, the 4-indyl, the 5-indyl, the 6-indyl, the 7-indyl, the 1-isoindolyl, the 2-isoindolyl, the 3-isoindolyl, the 4-isoindolyl, the 5-isoindolyl, the 6-isoindolyl, the 7-isoindolyl, the 2-furyl, the 3-furyl, the 2-benzofuranyl, the 3-benzofuranyl, the 4-benzofuranyl, the 5-benzofuranyl, the 6-benzofuranyl, the 7-benzofuranyl, the 1-isobenzofuran-base, the 3-isobenzofuran-base, the 4-isobenzofuran-base, the 5-isobenzofuran-base, the 6-isobenzofuran-base, the 7-isobenzofuran-base, the 2-quinolyl, the 3-quinolyl, the 4-quinolyl, the 5-quinolyl, the 6-quinolyl, the 7-quinolyl, the 8-quinolyl, the 1-isoquinolyl, the 3-isoquinolyl, the 4-isoquinolyl, the 5-isoquinolyl, the 6-isoquinolyl, the 7-isoquinolyl, the 8-isoquinolyl, 2-quinoxalinyl (quinoxanyl), 5-quinoxalinyl (quinoxanyl), 6-quinoxalinyl (quinoxanyl), the 1-carbazyl, the 2-carbazyl, the 3-carbazyl, the 4-carbazyl, the 9-carbazyl, 1-coffee pyridine base, 2-coffee pyridine base, 3-coffee pyridine base, 4-coffee pyridine base, 6-coffee pyridine base, 7-coffee pyridine base, 8-coffee pyridine base, 9-coffee pyridine base, 10-coffee pyridine base, the 1-acridinyl, the 2-acridinyl, the 3-acridinyl, the 4-acridinyl, the 9-acridinyl, 1, the 7-phenanthrene is coughed up beautiful jade-2-base, 1, the 7-phenanthrene is coughed up beautiful jade-3-base, 1, the 7-phenanthrene is coughed up beautiful jade-4-base, 1, the 7-phenanthrene is coughed up beautiful jade-5-base, 1, the 7-phenanthrene is coughed up beautiful jade-6-base, 1, the 7-phenanthrene is coughed up beautiful jade-8-base, 1, the 7-phenanthrene is coughed up beautiful jade-9-base, 1, the 7-phenanthrene is coughed up beautiful jade-10-base, 1, the 8-phenanthrene is coughed up beautiful jade-2-base, 1, the 8-phenanthrene is coughed up beautiful jade-3-base, 1, the 8-phenanthrene is coughed up beautiful jade-4-base, 1, the 8-phenanthrene is coughed up beautiful jade-5-base, 1, the 8-phenanthrene is coughed up beautiful jade-6-base, 1, the 8-phenanthrene is coughed up beautiful jade-7-base, 1, the 8-phenanthrene is coughed up beautiful jade-9-base, 1, the 8-phenanthrene is coughed up beautiful jade-10-base, 1, the 9-phenanthrene is coughed up beautiful jade-2-base, 1, the 9-phenanthrene is coughed up beautiful jade-3-base, 1, the 9-phenanthrene is coughed up beautiful jade-4-base, 1, the 9-phenanthrene is coughed up beautiful jade-5-base, 1, the 9-phenanthrene is coughed up beautiful jade-6-base, 1, the 9-phenanthrene is coughed up beautiful jade-7-base, 1, the 9-phenanthrene is coughed up beautiful jade-8-base, 1, the 9-phenanthrene is coughed up beautiful jade-10-base, 1, the 10-phenanthrene is coughed up beautiful jade-2-base, 1, the 10-phenanthrene is coughed up beautiful jade-3-base, 1, the 10-phenanthrene is coughed up beautiful jade-4-base, 1, the 10-phenanthrene is coughed up beautiful jade-5-base, 2,9-phenanthrolines-1-base, 2, the 9-phenanthrene is coughed up beautiful jade-3-base, 2, the 9-phenanthrene is coughed up beautiful jade-4-base, 2, the 9-phenanthrene is coughed up beautiful jade-5-base, 2, the 9-phenanthrene is coughed up beautiful jade-6-base, 2, the 9-phenanthrene is coughed up beautiful jade-7-base, 2, the 9-phenanthrene is coughed up beautiful jade-8-base, 2, the 9-phenanthrene is coughed up beautiful jade-10-base, 2, the 8-phenanthrene is coughed up beautiful jade-1-base, 2, the 8-phenanthrene is coughed up beautiful jade-3-base, 2, the 8-phenanthrene is coughed up beautiful jade-4-base, 2, the 8-phenanthrene is coughed up beautiful jade-5-base, 2, the 8-phenanthrene is coughed up beautiful jade-6-base, 2, the 8-phenanthrene is coughed up beautiful jade-7-base, 2, the 8-phenanthrene is coughed up beautiful jade-9-base, 2, the 8-phenanthrene is coughed up beautiful jade-10-base, 2, the 7-phenanthrene is coughed up beautiful jade-1-base, 2, the 7-phenanthrene is coughed up beautiful jade-3-base, 2, the 7-phenanthrene is coughed up beautiful jade-4-base, 2, the 7-phenanthrene is coughed up beautiful jade-5-base, 2, the 7-phenanthrene is coughed up beautiful jade-6-base, 2, the 7-phenanthrene is coughed up beautiful jade-8-base, 2, the 7-phenanthrene is coughed up beautiful jade-9-base, 2, the 7-phenanthrene is coughed up beautiful jade-10-base, the 1-phenazinyl, the 2-phenazinyl, the 1-phenothiazinyl, the 2-phenothiazinyl, the 3-phenothiazinyl, the 4-phenothiazinyl, the lysivane base, the 1-phenoxazine group, the 2-phenoxazine group, the 3-phenoxazine group, the 4-phenoxazine group, the 10-phenoxazine group, the 2-oxazolyl, the 4-oxazolyl, the 5-oxazolyl, 2-oxadiazole base, 5-oxadiazole base, 3-furazan base (furazanyl), the 2-thienyl, the 3-thienyl, 2-picoline-1-base, 2-methylpyrrole-3-base, 2-methylpyrrole-4-base, 2-methylpyrrole-5-base, 3-methylpyrrole-1-base, 3-methylpyrrole-2-base, 3-methylpyrrole-4-base, 3-methylpyrrole-5-base, 2-tert-butyl group pyrroles-4-base, 3-(2-phenyl propyl) pyrroles one-1-base, 2-methyl isophthalic acid-indyl, 4-methyl isophthalic acid-indyl, 2-methyl-3-indyl, 4-methyl-3-indyl, the 2-tert-butyl group-1-indyl, the 4-tert-butyl group-1-indyl, the 2-tert-butyl group-3-indyl or the 4-tert-butyl group-3-indyl.
The synthetic method of organic electronic transmission of the present invention and/or hole barrier materials may further comprise the steps:
(1). under the room temperature, will have substituent R 4, R 5, R 4', R 5' 2-bromo-1-acetophenone, have substituent R 5, Ar 2, R 5', Ar 2' the bromo aryl methyl ketone or have substituent R 5, Ar 2, R 5', Ar 2' bromo aromatic heterocycle ethyl ketone and pyridine raw material, be that 1: 1 ratio is dissolved in the organic solvent with mol ratio, stir, filter and obtain pyridinium tribromide salt product;
(2). under inert gas shielding, the pyridinium tribromide salt product that step (1) is obtained and has substituent R 1Dialdehyde and have a substituent R 2, R 3, R 2', R 3' acetophenone, have substituent R 2, Ar 1, R 2', Ar 1' aryl methyl ketone or have substituent R 2, Ar 1, R 2', Ar 1' the aryl-heterocyclic ethyl ketone, be 2: 1: 2 mixed with mol ratio, and be mixed with the ammonium acetate of catalytic amount, mixture is dissolved in the glacial acetic acid refluxes then, filter out product, through column chromatography chromatogram or recrystallization, obtain the polyaryl substituted pyridine derivative;
Wherein: R 1, R 2, R 2', R 3, R 3', R 4, R 4', R 5, R 5', Ar 1, Ar 1', Ar 2, Ar 2' definition with the definition one class polyaryl substituted pyridine derivative molecular structure in R 1, R 2, R 2', R 3, R 3', R 4, R 4', R 5, R 5', Ar 1, Ar 1', Ar 2, Ar 2'.
Described organic solvent is methyl alcohol, ethanol, oxolane, carrene or dioxane etc.
Organic electronic transmission of the present invention and/or hole barrier materials can be used as the electron transfer layer and/or the hole barrier layer material of organic electroluminescence device, be used to prepare organic electroluminescence device, be a kind of extraordinary royal purple light, blue light, green glow, fluorescence, gold-tinted, orange light, ruddiness, near-infrared fluorescent and phosphorescence device, especially blue organic electroluminescence device, and have good stability and long-life.The thickness of described electron transfer layer only is 35nm.
Organic electronic transmission of the present invention and/or hole barrier materials also can be used as the organic light emission layer material of organic electroluminescence device.
Described organic electroluminescence device all has very big purposes in organic integration circuit, organic solar batteries, organic laser or organic sensor.
The electron transfer layer of described organic electroluminescence device and/or hole blocking layer can be with being coated with or the method for vacuum steaming degree makes, and the structure of device is: anode/hole transmission layer/organic luminous layer/electron transfer layer/negative electrode.
The preferred implementation of fabricate devices:
The typical structure of OLED device is: substrate/anode/hole transmission layer (HTL)/organic luminous layer/electron transfer layer (ETL)/negative electrode.
Substrate is transparent, can be glass or flexible substrate, and flexible substrate adopts a kind of material in polyesters, the poly-phthalimide compounds; Anode layer can adopt inorganic material or organic conductive polymer, and inorganic material is generally tin indium oxide (hereinafter to be referred as ITO).The higher metals of work function such as metal oxide such as zinc oxide, zinc tin oxide or gold, copper, silver, the optimized ITO that is chosen as, organic conductive polymer are preferably a kind of material in poly-saliva fen/polyvinylbenzenesulfonic acid sodium (hereinafter to be referred as PEDOT:PSS), the polyaniline (hereinafter to be referred as PANI).Cathode layer generally adopts lower metal or a kind of and copper in them, gold or the silver-colored alloys of work function such as lithium, magnesium, calcium, strontium, aluminium or indium, or the electrode layer that alternately forms of above-mentioned metal or alloy and metal fluoride, the present invention is preferably LiF layer and Mg:Ag alloy-layer successively; Hole transmission layer generally adopts the tri-arylamine group material, and the present invention is preferably N, N '-two-(1-naphthyl)-N, N '-diphenyl-1,1-xenyl-4,4-diamines (NPB); Electron transfer layer is generally metal organic complex, close gallium (III) (the following Alq3 that is called for short respectively as three (oxine) aluminium, three (oxine) gallium, (the adjacent amine phenol of salicylidene)-(oxine), Gaq3, Ga (Saph-q)), also can be adjacent phenanthrene and cough up the beautiful jade class, as 4,7-diphenyl-1, the adjacent phenanthrene of 10-is coughed up beautiful jade (hereinafter to be referred as Bphen) etc., the preferred polyaryl substituted pyridine derivative of the present invention of the present invention has been obtained than the better device effect of foregoing several classical electron transferring materials as electron transfer layer; Organic luminous layer generally can adopt small molecule material, can doping fluorescent material or phosphorescent coloring, and the preferred material of main part of the present invention is ADN, TBP, Alq3, Gaq3, Ga (Saph-q).
Figure S2007101760098D00121
Can prepare a series of organic electroluminescence device of the present invention in accordance with the following methods:
(1) divide several steps to clean the glass substrate that has anode with cleaning agent, deionized water and organic solution;
(2) hole transmission layer of the method evaporation device by vacuum evaporation;
(3) continue the luminescent layer of evaporation device again;
(4) electron transfer layer of continuation evaporation device;
(5) method by evaporation or sputter prepares metallic cathode again.
OLED prepares enforcement:
Glass plate sonicated in commercial cleaning agent of ITO transparency conducting layer will be coated with, in deionized water, wash, at acetone: ultrasonic oil removing in the alcohol mixed solvent, under clean environment, be baked to and remove moisture content fully, with ultraviolet light cleaning machine irradiation 10 minutes, and with low energy cation bundle bombarded surface.
The above-mentioned glass substrate that has anode is placed in the vacuum chamber, be evacuated to 1 * 10 -5～9 * 10 -3Pa, first evaporation CuPc15nm on above-mentioned anode tunic continues evaporation NPB as hole transmission layer, and evaporation speed is that 0.1nm/s. evaporation thickness is 75nm;
On hole transmission layer, continue evaporation one deck and be doped with the luminescent layer of the TBP of compd A DN as device, the evaporation speed ratio of ADN and TBP is 1: 100, and the doping content of ADN in TBP is 1wt%, the total speed of its evaporation is 0.1nm/s, and the evaporation total film thickness is 30nm;
Continue the electron transfer layer of the prepared material of evaporation one deck the present invention as device again, its evaporation speed is 0.1nm/s, and the evaporation total film thickness is 35nm.
At last, evaporation LiF layer and Mg:Ag alloy-layer are as the cathode layer of device on above-mentioned electron transfer layer, and wherein the thickness of LiF layer is 0.5nm, and the evaporation speed of Mg:Ag alloy-layer is 2.0～3.0nm/s, and thickness is 100nm.
The present invention adopts easy method to synthesize a class polyaryl substituted pyridine derivative, and makes electric transmission and/or hole barrier materials has been made blue-light device with this polyaryl substituted pyridine derivative.This type of polyaryl substituted pyridine derivative has high IP/EA value, and has high quantum yield, has high brightness, is electron transport material and/or hole barrier materials that a class has the high hole blocking capability; Have high Tg temperature, can effectively suppress the crystalline condition of material, improve film forming, improve the performance of device.With respect to PBD, the material conjugate length that contains among the present invention increases, and fusing point greatly improves; The most important thing is that electron transport ability significantly strengthens, thereby improved the combination property of electroluminescent device.When being used for organic electroluminescence device, obtained gratifying result aspect the efficient of the device of making under brightness, current density and high current density, wherein a kind of combination property obviously is better than the BCP of present extensive use, thereby has obtained a kind of electric transmission of function admirable and/or the organic electroluminescence device of hole barrier materials.
In order to understand the content of patent of the present invention better, will further specify technical scheme of the present invention by specific embodiment below, but be not limited thereto.
Embodiment
Embodiment 1.1, the preparation of two (4-(2-phenyl-6-p-tolyl-3-5-flumethiazine)) benzene (BPTTPB) of 4-
Figure S2007101760098D00131
The first step: getting mol ratio and be 1 2-bromo-1-(4-trifluoromethyl) ethyl ketone and pyridine is raw material, at room temperature stirs 11 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 90%;
Second step: under the condition of nitrogen protection; with first step product; terephthalaldehyde and melilotal (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 50%.
m/z：700.23(100.0％)，701.23(48.3％)，702.24(11.2％)，703.24(1.8％)。
The OLED device preparation of compd B PTTPB
Device architecture:
ITO/CuPc(15nm)/NPB(75nm)/ADN:TBP(30nm)/
BPTTPB(35nm)/LiF(0.5nm)/MgAg(10∶1?100nm)
The device performance index is as follows:
Chromaticity coordinate: (X=0.15, Y=0.22);
Play bright voltage: 4.2V;
High-high brightness: 19800cd/m 2(12V);
Luminous efficiency: 4.5cd/A.
Embodiment 2.1, the preparation of two (4-(6-(4-xenyl)-2-phenyl-3-5-flumethiazine)) benzene (BBPTPB) of 4-
Figure S2007101760098D00141
The first step: get mol ratio and be 1 2-bromo-1-(4-trifluoromethyl) ethyl ketone, pyridine is a raw material, at room temperature stirs 12 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 90%;
Second step: under the condition of nitrogen protection; with first step product; terephthalaldehyde and p-phenylacetophenone (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 55%.
m/z：824.26(100.0％)，825.27(58.8％)，826.27(17.0％)，827.27(3.3％)。
Embodiment 3.4,4 '-(1, the 4-phenylene) two (2-phenyl-6-p-methylphenyl pyridine nitrile) preparation (PBPTNN)
Figure S2007101760098D00142
The first step: get mol ratio and be 1 4-(2-bromo acetyl group) benzene nitrile, pyridine is a raw material, at room temperature stirs 10 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 85%;
Second step: under the condition of nitrogen protection; with first step product; terephthalaldehyde and melilotal (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 60%.
m/z：614.25(100.0％)，615.25(47.9％)，616.25(11.8％)，617.26(1.7％)，615.24(1.5％)。
The OLED device preparation of Compound P BPTNN
Device architecture:
ITO/CuPc(15nm)/NPB(75nm)/ADN:TBP(30nm)/
PBPTNN(35nm)/LiF(0.5nm)/MgAg(10∶1?100nm)
The device performance index is as follows:
Chromaticity coordinate: (X=0.15, Y=0.22);
Play bright voltage: 4.0V;
High-high brightness: 19500cd/m 2(12V);
Luminous efficiency: 4.2cd/A.
Embodiment 4.4,4 '-(1, the 4-phenylene) two (6-(4-tert-butyl benzene)-2-phenylpyridine nitrile) preparation (PBPNN)
Figure S2007101760098D00151
The first step: get mol ratio and be 1 4-(2-bromo acetyl group) benzene nitrile, pyridine is a raw material, at room temperature stirs 8 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 85%;
Second step: under the condition of nitrogen protection; with first step product; terephthalaldehyde and p-tert.-butyl acetophenone (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 50%.
m/z：698.34(100.0％)，699.34(55.6％)，700.35(14.6％)，701.35?(2.6％)。
Embodiment 5.4,4 '-(1, the 4-phenylene) two (6-(4-xenyl)-2-phenylpyridine diethylester) preparation (PBBPN)
Figure S2007101760098D00161
The first step: get mol ratio and be 1 4-(2-bromo acetyl group) ethyl benzoate, pyridine is a raw material, at room temperature stirs 9 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 95%;
Second step: under the condition of nitrogen protection; with first step product; terephthalaldehyde and p-phenylacetophenone (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 55%.
m/z：832.33(100.0％)，833.33(63.6％)，834.34(19.8％)，835.34(4.6％)，834.33(1.3％)。
Embodiment 6.4,4 '-(1, the 4-phenylene) two (2-phenyl-6-p-methylphenyl pyridine-3,5-dintrile) preparation (PBPTDN)
Figure S2007101760098D00162
The first step: get mol ratio and be 1 4-(2-acetyl bromide) benzene nitrile, pyridine is a raw material, at room temperature stirs 12 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 90%;
Second step: under the condition of nitrogen protection; with first step product; terephthalaldehyde and ω-cyano group-4-methyl acetophenone (mol ratio is 2: 1: 2) adds in the three-necked bottle, adds an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 45%.
m/z：664.24(100.0％)，665.24(50.1％)，666.24(13.2％)，665.23(2.2％)，667.25(2.0％)。
Embodiment 7.4,4 '-(1, the 4-phenylene) two (2-(4-tert-butyl-phenyl)-6-phenylpyridine-3,5-dintrile) preparation (PBBPD)
The first step: get mol ratio and be 1 4-(2-acetyl bromide) benzene nitrile, pyridine is a raw material, at room temperature stirs 12 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 90%;
Second step: under the condition of nitrogen protection; with first step product; terephthalaldehyde and ω-cyano group-4-tert-butyl benzene ethyl ketone (mol ratio is 2: 1: 2) adds in the three-necked bottle, adds an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 50%.
m/z：748.33(100.0％)，749.33(58.5％)，750.34(15.8％)，751.34(3.2％)，750.33(1.3％)。
The OLED device preparation of Compound P BBPD
Device architecture:
ITO/CuPc(15nm)/NPB(75nm)/ADN:TBP(30nm)/
PBBPD(35nm)/LiF(0.5nm)/MgAg(10∶1?100nm)
The device performance index is as follows:
Chromaticity coordinate: (X=0.15, Y=0.22);
Play bright voltage: 4.0V;
High-high brightness: 22000cd/m 2(12V);
Luminous efficiency: 4.4cd/A.
Embodiment 8.1, the preparation of two (4-(6-(2-furyl)-2-phenyl-3-5-flumethiazine)) benzene (BFPPB) of 4-
The first step: get mol ratio and be 1 2-bromo-1-(4-trifluoromethyl) ethyl ketone, pyridine is a raw material, at room temperature stirs 8 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 90%;
Second step: under the condition of nitrogen protection; with first step product; terephthalaldehyde and 4-(2-furyl) acetophenone (mol ratio is 2: 1: 2) adds in the three-necked bottle; add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring, keeping temperature is 120 ℃～140 ℃; refluxed 24 hours; filter out product,, obtain target product with high purity 48% through column chromatography chromatogram or recrystallization.
m/z：652.16(100.0％)，653.16(42.2％)，654.17(8.4％)，655.17(1.3％)。
Embodiment 9.1, the preparation of two (4-(2-phenyl-6-p-tolyl-3-5-flumethiazine)) benzene (BPTFPB) of 3-
Figure S2007101760098D00182
The first step: get mol ratio and be 1 2-bromo-1-(4-trifluoromethyl) ethyl ketone, pyridine is a raw material, at room temperature stirs 10 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 90%;
Second step: under the condition of nitrogen protection; with first step product; m-terephthal aldehyde and melilotal (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 60%.
m/z：700.23(100.0％)，701.23(48.3％)，702.24(11.2％)，703.24(1.8％)。
The OLED device preparation of compd B PTFPB
Device architecture:
ITO/CuPc(15nm)/NPB(75nm)/ADN:TBP(30nm)/
BPTFPB(35nm)/LiF(0.5nm)/MgAg(10∶1?100nm)
The device performance index is as follows:
Chromaticity coordinate: (X=0.15, Y=0.22);
Play bright voltage: 3.9V;
High-high brightness: 19000cd/m 2(12V);
Luminous efficiency: 4.0cd/A.
Embodiment 10.1, the preparation of two (4-(6-(4-methoxyl group)-2-phenyl-3-5-flumethiazine)) benzene (BMPTPB) of 3-
Figure S2007101760098D00191
The first step: get mol ratio and be 1 2-bromo-1-(4-trifluoromethyl) ethyl ketone, pyridine is a raw material, at room temperature stirs 8 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 90%;
Second step: under the condition of nitrogen protection; with first step product; m-terephthal aldehyde and acetanisole (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 55%.
m/z：732.22(100.0％)，733.22(48.3％)，734.23(11.7％)，735.23(1.9％)。
Embodiment 11.4,4 '-(1, the 3-phenylene) two (2-phenyl-6-p-methylphenyl pyridine nitrile) preparation (PBPTCN)
Figure S2007101760098D00201
The first step: get mol ratio and be 1 4-(2-bromo acetyl group) benzene nitrile, pyridine is a raw material, at room temperature stirs 7 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 85%;
Second step: under the condition of nitrogen protection; with first step product; m-terephthal aldehyde and melilotal (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 45%.
m/z：614.25(100.0％)，615.25(47.9％)，616.25(11.8％)，617.26(1.7％)，615.24(1.5％)。
Embodiment 12.4,4 '-(1, the 3-phenylene) two (6-(4-tert-butyl benzene)-2-phenylpyridine nitrile) preparation (PBTPNN)
Figure S2007101760098D00202
The first step: get mol ratio and be 1 4-(2-bromo acetyl group) benzene nitrile, pyridine is a raw material, at room temperature stirs 11 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 85%;
Second step: under the condition of nitrogen protection; with first step product; m-terephthal aldehyde and p-tert.-butyl acetophenone (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 55%.
m/z：698.34(100.0％)，699.34(55.6％)，700.35(14.6％)，701.35(2.6％)。
Embodiment 13.4,4 '-(1, the 3-phenylene) two (6-(4-methoxybenzene)-2-phenylpyridine diethylester) preparation (PBMPNN)
The first step: get mol ratio and be 1 4-(2-bromo acetyl group) ethyl benzoate, pyridine is a raw material, at room temperature stirs 9 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 95%;
Second step: under the condition of nitrogen protection; with first step product; m-terephthal aldehyde and acetanisole (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 60%.
m/z：740.29(100.0％)，741.29(53.3％)，742.30(13.6％)，743.30(2.9％)，742.29(1.6％)。
Embodiment 14.4,4 '-(1, the 3-phenylene) two (2,6-diphenyl-5-5-flumethiazine nitrile) preparation (PBDFNN)
Figure S2007101760098D00212
The first step: get mol ratio and be 1 4-(2-bromo acetyl group) benzene nitrile, pyridine is a raw material, at room temperature stirs 10 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 90%;
Second step: under the condition of nitrogen protection; with first step product; m-terephthal aldehyde and ω-trifluoromethyl acetophenone (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 60%.
m/z：722.19(100.0％)，723.19(49.1％)，724.20(11.2％)，725.20(1.7％)。
The OLED device preparation of Compound P BDFNN
Device architecture:
ITO/CuPc(15nm)/NPB(75nm)/ADN:TBP(30nm)/
PBDFNN(35nm)/LiF(0.5nm)/MgAg(10∶1?100nm)。
The device performance index is as follows:
Chromaticity coordinate: (X=0.15, Y=0.22);
Play bright voltage: 4.4V;
High-high brightness: 20050cd/m 2(12V);
Luminous efficiency: 4.2cd/A.
Embodiment 15.4,4 '-(1, the 3-phenylene) two (2-(4-tert-butyl-phenyl)-6-phenylpyridine-3,5-dintrile) preparation (PBTPD)
Figure S2007101760098D00221
The first step: get mol ratio and be 1 4-(2-acetyl bromide) benzene nitrile, pyridine is a raw material, at room temperature stirs 12 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 90%;
Second step: under the condition of nitrogen protection; with first step product; m-terephthal aldehyde and ω-cyano group-4-tert-butyl benzene ethyl ketone (mol ratio is 2: 1: 2) adds in the three-necked bottle, adds an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 50%.
m/z：748.33(100.0％)，749.33(58.5％)，750.34(15.8％)，751.34(3.2％)，750.33(1.3％)。
Embodiment 16.1, the preparation of two (4-(6-(2-furyl)-2-phenyl-3-5-flumethiazine)) benzene (BFPTPB) of 3-
Figure S2007101760098D00231
The first step: get mol ratio and be 1 2-bromo-1-(4-trifluoromethyl) ethyl ketone, pyridine is a raw material, at room temperature stirs 12 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 90%;
Second step: under the condition of nitrogen protection; with first step product; m-terephthal aldehyde and 4-(2-furyl) acetophenone (mol ratio is 2: 1: 2) adds in the three-necked bottle, adds an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 50%.
m/z：652.16(100.0％)，653.16(42.2％)，654.17(8.4％)，655.17(1.3％)。
Embodiment 17.1, the preparation of two (4-(6-(4-methoxyl group)-2-phenyl-3-5-flumethiazine)) benzene (BPTPB) of 2-
Figure S2007101760098D00232
The first step: get mol ratio and be 1 2-bromo-1-(4-trifluoromethyl) ethyl ketone, pyridine is a raw material, at room temperature stirs 8 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 90%;
Second step: under the condition of nitrogen protection; with first step product; OPA and acetanisole (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 45%.
m/z：732.22(100.0％)，733.22(48.3％)，734.23(11.7％)，735.23(1.9％)。
Embodiment 18.1, the preparation of two (4-(6-(4-xenyl)-2-phenyl-3-5-flumethiazine)) benzene (BPPTPB) of 2-
Figure S2007101760098D00241
The first step: get mol ratio and be 1 2-bromo-1-(4-trifluoromethyl) ethyl ketone, pyridine is a raw material, at room temperature stirs 10 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 90%;
Second step: under the condition of nitrogen protection; with first step product; OPA and p-phenylacetophenone (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 60%.
m/z：824.26(100.0％)，825.27(58.8％)，826.27(17.0％)，827.27(3.3％)。
The OLED device preparation of compd B PPTPB
Device architecture:
ITO/CuPc(15nm)/NPB(75nm)/ADN:TBP(30nm)/
BPPTPB(35nm)/LiF(0.5nm)/MgAg(10∶1?100nm)。
The device performance index is as follows:
Chromaticity coordinate: (X=0.15, Y=0.22);
Play bright voltage: 4.5V;
High-high brightness: 20020cd/m 2(12V);
Luminous efficiency: 4.8cd/A.
Embodiment 19.4,4 '-(1, the 2-phenylene) two (6-(4-xenyl)-2-phenylpyridine nitrile) preparation (PBCPNN)
Figure S2007101760098D00251
The first step: get mol ratio and be 1 4-(2-bromo acetyl group) benzene nitrile, pyridine is a raw material, at room temperature stirs 11 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 85%;
Second step: under the condition of nitrogen protection; with first step product; OPA and p-phenylacetophenone (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 65%.
m/z：738.28(100.0％)，739.28(60.3％)，740.29(17.0％)，741.29(3.2％)。
Embodiment 20.4,4 '-(1, the 2-phenylene) two (6-(4-tert-butyl benzene)-2-phenylpyridine nitrile) preparation (PBTNN)
Figure S2007101760098D00252
The first step: get mol ratio and be 1 4-(2-bromo acetyl group) benzene nitrile, pyridine is a raw material, at room temperature stirs 12 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 85%;
Second step: under the condition of nitrogen protection; with first step product; OPA and p-tert.-butyl acetophenone (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 55%.
m/z：698.34(100.0％)，699.34(55.6％)，700.35(14.6％)，701.35(2.6％)。
Embodiment 21.4,4 '-(1, the 2-phenylene) two (6-(4-methoxybenzene)-2-phenylpyridine diethylester) preparation (PBNN)
Figure S2007101760098D00261
The first step: get mol ratio and be 1 4-(2-bromo acetyl group) ethyl benzoate, pyridine is a raw material, at room temperature stirs 10 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 95%;
Second step: under the condition of nitrogen protection; with first step product; OPA and acetanisole (mol ratio is 2: 1: 2) add in the three-necked bottle, add an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 60%.
m/z：740.29(100.0％)，741.29(53.3％)，742.30(13.6％)，743.30(2.9％)，742.29(1.6％)。
The OLED device preparation of Compound P BNN
Device architecture:
ITO/CuPc(15nm)/NPB(75nm)/ADN:TBP(30nm)/
PBNN(35nm)/LiF(0.5nm)/MgAg(10∶1?100nm)。
The device performance index is as follows:
Chromaticity coordinate: (X=0.15, Y=0.22);
Play bright voltage: 4.5V;
High-high brightness: 20020cd/m 2(12V);
Luminous efficiency: 4.8cd/A.
Embodiment 22.4,4 '-(1, the 2-phenylene) two (2-phenyl-6-p-methylphenyl pyridine-3,5-dintrile) preparation (PBPTDB)
Figure S2007101760098D00271
The first step: get mol ratio and be 1 4-(2-acetyl bromide) benzene nitrile, pyridine is a raw material, at room temperature stirs 11 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 85%;
Second step: under the condition of nitrogen protection; with first step product; OPA and ω-cyano group-4-methyl acetophenone (mol ratio is 2: 1: 2) adds in the three-necked bottle, adds an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 45%.
m/z：664.24(100.0％)，665.24(50.1％)，666.24(13.2％)，665.23(2.2％)，667.25(2.0％)。
Embodiment 23.4,4 '-(1, the 2-phenylene) two (2-(4-tert-butyl benzene-6-phenylpyridine-3,5-dintrile) preparations (PBPPD)
Figure S2007101760098D00272
The first step: get mol ratio and be 1 4-(2-acetyl bromide) benzene nitrile, pyridine is a raw material, at room temperature stirs 12 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 90%;
Second step: under the condition of nitrogen protection; with first step product; OPA and ω-cyano group-4-tert-butyl benzene ethyl ketone (mol ratio is 2: 1: 2) adds in the three-necked bottle, adds an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 50%.
m/z：748.33(100.0％)，749.33(58.5％)，750.34(15.8％)，751.34(3.2％)，750.33(1.3％)。
The OLED device preparation of Compound P BPPD
Device architecture:
ITO/CuPc(15nm)/NPB(75nm)/ADN:TBP(30nm)/
PBPPD(35nm)/LiF(0.5nm)/MgAg(10∶1?100nm)。
The device performance index is as follows:
Chromaticity coordinate: (X=0.15, Y=0.22);
Play bright voltage: 3.8V;
High-high brightness: 20120cd/m 2(12V);
Luminous efficiency: 5.0cd/A.
Embodiment 24.1, the preparation of two (4-(6-(2-furyl)-2-phenyl-3-5-flumethiazine)) benzene (BFTPB) of 2-
Figure S2007101760098D00281
The first step: get mol ratio and be 1 2-bromo-1-(4-trifluoromethyl) ethyl ketone, pyridine is a raw material, at room temperature stirs 12 hours, filters, and massive laundering promptly gets corresponding pyridine bromine salt, productive rate about 90%;
Second step: under the condition of nitrogen protection; with first step product; OPA and 4-(2-furyl) acetophenone (mol ratio is 2: 1: 2) adds in the three-necked bottle, adds an amount of glacial acetic acid and ammonium acetate then, the powerful stirring; keeping temperature is 120 ℃～140 ℃; refluxed 24 hours, and filtered out product, through column chromatography chromatogram or recrystallization; obtain target product with high purity, productive rate about 65%.
m/z：652.16(100.0％)，653.16(42.2％)，654.17(8.4％)，655.17(1.3％)。
More than listed embodiment all can be used in organic transistor, organic integration circuit, organic solar batteries, organic laser or the organic sensor.
Although describe the present invention in conjunction with the preferred embodiments, but the present invention is not limited to the foregoing description, should be appreciated that under the guiding of the present invention's design, those skilled in the art can carry out various modifications and improvement, and claims have been summarized scope of the present invention.

Claims (10)

1. an organic electronic transmits and/or hole barrier materials, it is characterized in that, this organic electronic transmission and/or hole barrier materials are the polyaryl substituted pyridine derivatives, and it has following molecular structure:
Figure FSB00000278855300011
Wherein:
R 1, R 3, R 3', R 4, R 4' substituting group can be identical or different, independently be selected from hydrogen respectively, have the replacement or the unsubstituted alkyl of 1 to 20 carbon atom, replacement or unsubstituted cycloalkyl with 5 to 20 carbon atoms, have 1 to 20 carbon atom alkoxyl, have 6 to 60 carbon atoms aralkyl, have 6 to 50 ring carbon atoms aryl, have the aryloxy group of 6 to 50 annular atomses or have a kind of in the aromatic heterocyclic group of 5 to 50 annular atomses;
R 2, R 2', R 5, R 5' substituting group can be identical or different, independently be selected from carboxyl, fluoro methyl, cyano group, nitro respectively or have a kind of in the ester group of 2 to 20 carbon atoms;
Ar 1, Ar 1', Ar 2, Ar 2' substituting group can be identical or different, independently be selected from aryl respectively or have a kind of in the aromatic heterocyclic group of 5 to 50 annular atomses with 6 to 50 ring carbon atoms.
2. organic electronic transmission according to claim 1 and/or hole barrier materials is characterized in that: described R 1, R 3, R 3', R 4, R 4' in the not substituted alkyl with 1 to 20 carbon atom be methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl or n-octyl;
Described R 1, R 3, R 3', R 4, R 4' in the substituted alkyl with 1 to 20 carbon atom be methylol, the 1-ethoxy, the 2-ethoxy, 2-hydroxyl isobutyl group, 1, the 2-dihydroxy ethyl, 1,3-dihydroxy isopropyl, 2, the 3 one dihydroxy-tert-butyl group, 1,2,3 one trihydroxy propyl group, chloromethyl, the 1-chloroethyl, the 2-chloroethyl, 2-chlorine isobutyl group, 1, the 2-Dichloroethyl, 1,3-two chloro isopropyls, 2, the 3-two chloro-tert-butyl groups, 1,2,3-three chloropropyls, bromomethyl, the 1-bromoethyl, the 2-bromoethyl, 2-melts isobutyl group, 1,2-two bromoethyls, 1,3-dibromo isopropyl, 2, the 3-two bromo-tert-butyl groups, 1,2,3-three bromopropyls, iodomethyl, 1-iodine ethyl, 2-iodine ethyl, 2-iodine isobutyl group, 1,2-diiodo-ethyl, 1,3-diiodo-isopropyl, 2, the 3-two iodo-tert-butyl groups, 1,2,3-triiodo propyl group, amino methyl, the 1-amino-ethyl, the 2-amino-ethyl, 2-aminoisobutyric base, 1, the 2-diamino ethyl, 1,3-diaminourea isopropyl, 2,3-diaminourea-tert-butyl group or 1,2,3-triamido propyl group;
Described R 1, R 3, R 3', R 4, R 4' in the unsubstituted cycloalkyl with 5 to 20 carbon atoms be cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl;
Described R 1, R 3, R 3', R 4, R 4' in the cycloalkyl of replacement with 5 to 20 carbon atoms be 4-methylcyclohexyl, adamantyl or norborneol alkyl;
Described R 1, R 3, R 3', R 4, R 4' in the alkoxyl with 1 to 20 carbon atom be by-group that OR represents, wherein the group represented of R is an alkyl, alkyl is a methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, methylol, the 1-ethoxy, the 2-ethoxy, 2-hydroxyl isobutyl group, 1, the 2-dihydroxy ethyl, 1,3-two chloro isopropyls, 2, the 3-two chloro-tert-butyl groups, 1,2,3-three chloropropyls, bromomethyl, the 1-bromoethyl, the 2-bromoethyl, 2-bromine isobutyl group, 1,2-two bromoethyls, 1,3-dibromo isopropyl, 2, the 3-two bromo-tert-butyl groups, 1,2,3-three bromopropyls, iodomethyl, 1-iodine ethyl, 2-iodine ethyl, 2-iodine isobutyl iodide 1,2-diiodo-ethyl, 1,3-diiodo-isopropyl, 2, the 3-two iodos-tert-butyl group, 1,2,3-triiodo propyl group, iodomethyl, 1-iodine ethyl, 2-iodine ethyl, 2-iodine isobutyl group, 1,2-diiodo-ethyl, 1,3-diiodo-isopropyl, 2, the 3-two iodo-tert-butyl groups, 1,2,3-triiodo propyl group, amino methyl, the 1-amino-ethyl, the 2-amino-ethyl, 2-aminoisobutyric base, 1, the 2-diamino ethyl, 1,3-diaminourea isopropyl, 2,3-diaminourea-tert-butyl group, 1,2,3-triamido propyl group, cyano methyl, the 1-cyano ethyl, the 2-cyano ethyl, 2-cyano group isobutyl group, 1,2-dicyano ethyl, 1,3-dicyano isopropyl, 2,3-dicyano-tert-butyl group, 1,2,3-tricyano propyl group, the nitro methyl, the 1-nitro-ethyl, the 2-nitro-ethyl, 2-nitro isobutyl group, 1,2-dinitro ethyl, 1,3-dinitro isopropyl, 2,3-dinitro-tert-butyl group or 1,2,3-trinitro-propyl group;
Described R 1, R 3, R 3', R 4, R 4' in have 6 to 60 carbon atoms aralkyl be benzyl, the 1-phenylethyl, the 2-phenylethyl, 1-propyloxy phenyl base, 2-propyloxy phenyl base, the phenyl tert-butyl group, the Alpha-Naphthyl methyl, 1-Alpha-Naphthyl ethyl, 2-Alpha-Naphthyl ethyl, 1-Alpha-Naphthyl isopropyl, 2-Alpha-Naphthyl isopropyl, the betanaphthyl methyl, 1-betanaphthyl ethyl, 2-betanaphthyl ethyl, 1-betanaphthyl isopropyl, 2-betanaphthyl isopropyl, 1-pyrrole radicals methyl, 2-(1-pyrrole radicals) ethyl, to methyl-benzyl, between methyl-benzyl, adjacent methyl-benzyl, p-chlorobenzyl, the m-chloro benzyl, o-chlorobenzyl, to bromobenzyl, between bromobenzyl, adjacent bromobenzyl, to the iodine benzyl, between the iodine benzyl, adjacent iodine benzyl, PAB, between aminobenzyl, adjacent aminobenzyl, to nitrobenzyl, between nitrobenzyl, adjacent nitrobenzyl, to the cyano group benzyl, between the cyano group benzyl, o-cyanobenzyl, 1-chloro-2-propyloxy phenyl base or trityl;
Described R 1, R 3, R 3', R 4, R 4' in have 6 to 50 ring carbon atoms aryl be phenyl, the 1-naphthyl, the 2-naphthyl, the 1-anthryl, the 2-anthryl, the 9-anthryl, the 1-phenanthryl, the 2-phenanthryl, the 3-phenanthryl, the 4-phenanthryl, the 9-phenanthryl, 1-aphthacene base, 2-aphthacene base, 9-aphthacene base, the 1-pyrenyl, the 2-pyrenyl, the 4-pyrenyl, the 2-xenyl, the 3-xenyl, the 4-xenyl, para-terpheny-4-base, para-terpheny-3-base, para-terpheny-2-base, meta-terphenyl-4-base, meta-terphenyl-3-base, meta-terphenyl-2-base, o-tolyl, between tolyl, p-methylphenyl, to tert-butyl-phenyl, right-(2-phenyl propyl) phenyl, 3-methyl-2-naphthyl, 4-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-anthryl, 4 '-methyl biphenyl or 4 "-tert-butyl group-para-terpheny-4-base;
Described R 1, R 3, R 3', R 4, R 4' in have 6 to 50 annular atomses aryloxy group be by-group that OAr represents, wherein the group represented of Ar is an aromatic group, aromatic group is a phenyl, the 1-naphthyl, the 2-naphthyl, the 1-anthryl, the 2-anthryl, the 9-anthryl, the 1-phenanthryl, the 2-phenanthryl, the 3-phenanthryl, the 4-phenanthryl, the 9-phenanthryl, 1-aphthacene base, 2-aphthacene base, 9-aphthacene base, the 1-pyrenyl, the 2-pyrenyl, the 4-pyrenyl, the 2-xenyl, the 3-xenyl, the 4-xenyl, para-terpheny-4-base, para-terpheny-3-base, para-terpheny-2-base, meta-terphenyl-4-base, meta-terphenyl-3-base, meta-terphenyl-2-base, o-tolyl, between tolyl, p-methylphenyl, to tert-butyl-phenyl, right-(2-phenyl propyl) phenyl, 3-methyl-2-naphthyl, 4-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-naphthyl, 4 '-methyl biphenyl; 4 "-the tert-butyl group-para-terpheny-4-base, the 2-pyrrole radicals, the 3-pyrrole radicals, pyridine radicals, the 2-pyridine radicals, the 3-pyridine radicals, the 4-pyridine radicals, the 2-indyl, the 3-indyl, the 4-indyl, the 5-indyl, the 6-indyl, the 7-indyl, the 1-isoindolyl, the 3-isoindolyl, the 4-isoindolyl, the 5-isoindolyl, the 6-isoindolyl, the 7-isoindolyl, the 2-furyl, the 3-furyl, the 2-benzofuranyl, the 3-benzofuranyl, the 4-benzofuranyl, the 5-benzofuranyl, the 6-benzofuranyl, the 7-benzofuranyl, the 1-isobenzofuran-base, the 3-isobenzofuran-base, the 4-isobenzofuran-base, the 5-isobenzofuran-base, the 6-isobenzofuran-base, 7-isobenzofuran-base 2-quinolyl, the 3-quinolyl, the 4-quinolyl, the 5-quinolyl, the 6-quinolyl, the 7-quinolyl, the 8-quinolyl, the 1-isoquinolyl, the 3-isoquinolyl, the 4-isoquinolyl, the 5-isoquinolyl, the 6-isoquinolyl, the 7-isoquinolyl, the 8-isoquinolyl, the 2-quinoxalinyl, the 5-quinoxalinyl, the 6-quinoxalinyl, the 1-carbazyl, the 2-carbazyl, the 3-carbazyl, the 4-carbazyl, the 1-phenanthridinyl, the 2-phenanthridinyl, the 3-phenanthridinyl, the 4-phenanthridinyl, the 6-phenanthridinyl, the 7-phenanthridinyl, the 8-phenanthridinyl, the 9-phenanthridinyl, the 10-phenanthridinyl, the 1-acridinyl, the 2-acridinyl, the 3-acridinyl, the 4-acridinyl, the 9-acridinyl, 1, the 7-phenanthrene is coughed up beautiful jade-2-base, 1, the 7-phenanthrene is coughed up beautiful jade-3-base, 1, the 7-phenanthrene is coughed up beautiful jade-4-base, 1, the 7-phenanthrene is coughed up beautiful jade-5-base, 1, the 7-phenanthrene is coughed up beautiful jade-6-base, 1, the 7-phenanthrene is coughed up beautiful jade-8-base, 1, the 7-phenanthrene is coughed up beautiful jade-9-base, 1, the 7-phenanthrene is coughed up beautiful jade-10-base, 1, the 8-phenanthrene is coughed up beautiful jade-2-base, 1, the 8-phenanthrene is coughed up beautiful jade-3-base, 1, the 8-phenanthrene is coughed up beautiful jade-4-base, 1, the 8-phenanthrene is coughed up beautiful jade-5-base, 1, the 8-phenanthrene is coughed up beautiful jade-6-base, 1, the 8-phenanthrene is coughed up beautiful jade-7-base, 1, the 8-phenanthrene is coughed up beautiful jade-9-base, 1, the 8-phenanthrene is coughed up beautiful jade-10-base, 1, the 9-phenanthrene is coughed up beautiful jade-2-base, 1, the 9-phenanthrene is coughed up beautiful jade-3-base, 1, the 9-phenanthrene is coughed up beautiful jade-4-base, 1, the 9-phenanthrene is coughed up beautiful jade-5-base, 1, the 9-phenanthrene is coughed up beautiful jade-6-base, 1, the 9-phenanthrene is coughed up beautiful jade-7-base, 1, the 9-phenanthrene is coughed up beautiful jade-8-base, 1, the 9-phenanthrene is coughed up beautiful jade-10-base, 1, the 10-phenanthrene is coughed up beautiful jade-2-base, 1, the 10-phenanthrene is coughed up beautiful jade-3-base, 1, the 10-phenanthrene is coughed up beautiful jade-4-base, 1, the 10-phenanthrene is coughed up beautiful jade-5-base, 2, the 9-phenanthrene is coughed up beautiful jade-1-base, 2, the 9-phenanthrene is coughed up beautiful jade-3-base, 2, the 9-phenanthrene is coughed up beautiful jade-4-base, 2, the 9-phenanthrene is coughed up beautiful jade-5-base, 2, the 9-phenanthrene is coughed up beautiful jade-6-base, 2, the 9-phenanthrene is coughed up beautiful jade-7-base, 2, the 9-phenanthrene is coughed up beautiful jade _ 8-base, 2, the 9-phenanthrene is coughed up beautiful jade-10-base, 2, the 8-phenanthrene is coughed up beautiful jade-1-base, 2, the 8-phenanthrene is coughed up beautiful jade-3-base, 2, the 8-phenanthrene is coughed up beautiful jade-4-base, 2, the 8-phenanthrene is coughed up beautiful jade-5-base, 2, the 8-phenanthrene is coughed up beautiful jade-6-base, 2, the 8-phenanthrene is coughed up beautiful jade-7-base, 2, the 8-phenanthrene is coughed up beautiful jade-9-base, 2, the 8-phenanthrene is coughed up beautiful jade-10-base, 2, the 7-phenanthrene is coughed up beautiful jade-1-base, 2, the 7-phenanthrene is coughed up beautiful jade-3-base, 2, the 7-phenanthrene is coughed up beautiful jade-4-base, 2, the 7-phenanthrene is coughed up beautiful jade-5-base, 2, the 7-phenanthrene is coughed up beautiful jade-6-base, 2, the 7-phenanthrene is coughed up beautiful jade-8-base, 2, the 7-phenanthrene is coughed up beautiful jade-9-base, 2, the 7-phenanthrene is coughed up beautiful jade-10-base, the 1-phenazinyl, the 2-phenazinyl, the 1-phenothiazinyl, the 2-phenothiazinyl, the 3-phenothiazinyl, the 4-phenothiazinyl, the 1-phenoxazine group, the 2-phenoxazine group, the 3-phenoxazine group, the 4-phenoxazine group, the 2-oxazole. base, the 4-oxazolyl, the 5-oxazolyl, 2-oxadiazole base, 5-oxadiazole base, 3-furazan base, the 2-thienyl, the 3-thienyl, 2-methylpyrrole-1-base, 2-methylpyrrole-3-base, 2-methylpyrrole-4-base, 2-methylpyrrole-5-base, 3-methylpyrrole-1-base, 3-methylpyrrole-2-base, 3-methylpyrrole-4-base, 3-methylpyrrole-5-base, 2-tert-butyl group pyrroles-4-base, 3-(2-phenyl propyl) pyrroles-1-base, 2-methyl isophthalic acid-indyl, 4-methyl isophthalic acid-indyl, 2-methyl-3-indyl, 4-methyl-3-indyl, the 2-tert-butyl group-1-indyl, the 4-tert-butyl group-1-indyl, the 2-tert-butyl group-3-indyl or the 4-tert-butyl group-3-indyl;
Described R 1, R 3, R 3', R 4, R 4' in have 5 to 50 annular atomses aromatic heterocyclic group be the 1-pyrrole radicals, the 2-pyrrole radicals, the 3-pyrrole radicals, pyridine radicals, the 2-pyridine radicals, the 3-pyridine radicals, the 4-pyridine radicals, the 1-indyl, the 2-indyl, the 3-indyl, the 4-indyl, the 5-indyl, the 6-indyl, the 7-indyl, the 1-isoindolyl, the 2-isoindolyl, the 3-isoindolyl, the 4-isoindolyl, the 5-isoindolyl, the 6-isoindolyl, the 7-isoindolyl, the 2-furyl, the 3-furyl, the 2-benzofuranyl, the 3-benzofuranyl, the 4-benzofuranyl, the 5-benzofuranyl, the 6-benzofuranyl, the 7-benzofuranyl, the 1-isobenzofuran-base, the 3-isobenzofuran-base, the 4-isobenzofuran-base, the 5-isobenzofuran-base, the 6-isobenzofuran-base, the 7-isobenzofuran-base, the 2-quinolyl, the 3-quinolyl, the 4-quinolyl, the 5-quinolyl, the 6-quinolyl, the 7-quinolyl, the 8-quinolyl, the 1-isoquinolyl, the 3-isoquinolyl, the 4-isoquinolyl, the 5-isoquinolyl, the 6-isoquinolyl, the 7-isoquinolyl, the 8-isoquinolyl, the 2-quinoxalinyl, the 5-quinoxalinyl, the 6-quinoxalinyl, the 1-carbazyl, the 2-carbazyl, the 3-carbazyl, the 4-carbazyl, the 9-carbazyl, 1-coffee pyridine base, 2-coffee pyridine base, 3-coffee pyridine base, 4-coffee pyridine base, 6-coffee pyridine base, 7-coffee pyridine base, 8-coffee pyridine base, 9-coffee pyridine base, 10-coffee pyridine base, the 1-acridinyl, the 2-acridinyl, the 3-acridinyl, the 4-acridinyl, the 9-acridinyl, 1, the 7-phenanthrene is coughed up beautiful jade-2-base, 1, the 7-phenanthrene is coughed up beautiful jade-3-base, 1, the 7-phenanthrene is coughed up beautiful jade-4-base, 1, the 7-phenanthrene is coughed up beautiful jade-5-base, 1, the 7-phenanthrene is coughed up beautiful jade-6-base, 1, the 7-phenanthrene is coughed up beautiful jade-8-base, 1, the 7-phenanthrene is coughed up beautiful jade-9-base, 1, the 7-phenanthrene is coughed up beautiful jade-10-base, 1, the 8-phenanthrene is coughed up beautiful jade-2-base, 1, the 8-phenanthrene is coughed up beautiful jade-3-base, 1, the 8-phenanthrene is coughed up beautiful jade-4-base, 1, the 8-phenanthrene is coughed up beautiful jade-5-base, 1, the 8-phenanthrene is coughed up beautiful jade-6-base, 1, the 8-phenanthrene is coughed up beautiful jade-7-base, 1, the 8-phenanthrene is coughed up beautiful jade-9-base, 1, the 8-phenanthrene is coughed up beautiful jade-10-base, 1, the 9-phenanthrene is coughed up beautiful jade-2-base, 1, the 9-phenanthrene is coughed up beautiful jade-3-base, 1, the 9-phenanthrene is coughed up beautiful jade-4-base, 1, the 9-phenanthrene is coughed up beautiful jade-5-base, 1, the 9-phenanthrene is coughed up beautiful jade-6-base, 1, the 9-phenanthrene is coughed up beautiful jade-7-base, 1, the 9-phenanthrene is coughed up beautiful jade-8-base, 1, the 9-phenanthrene is coughed up beautiful jade-10-base, 1, the 10-phenanthrene is coughed up beautiful jade-2-base, 1, the 10-phenanthrene is coughed up beautiful jade-3-base, 1, the 10-phenanthrene is coughed up beautiful jade-4-base, 1, the 10-phenanthrene is coughed up beautiful jade-5-base, 2,9-phenanthrolines-1-base, 2, the 9-phenanthrene is coughed up beautiful jade-3-base, 2, the 9-phenanthrene is coughed up beautiful jade-4-base, 2, the 9-phenanthrene is coughed up beautiful jade-5-base, 2, the 9-phenanthrene is coughed up beautiful jade-6-base, 2, the 9-phenanthrene is coughed up beautiful jade-7-base, 2, the 9-phenanthrene is coughed up beautiful jade-8-base, 2, the 9-phenanthrene is coughed up beautiful jade-10-base, 2, the 8-phenanthrene is coughed up beautiful jade-1-base, 2, the 8-phenanthrene is coughed up beautiful jade-3-base, 2, the 8-phenanthrene is coughed up beautiful jade-4-base, 2, the 8-phenanthrene is coughed up beautiful jade-5-base, 2, the 8-phenanthrene is coughed up beautiful jade-6-base, 2, the 8-phenanthrene is coughed up beautiful jade-7-base, 2, the 8-phenanthrene is coughed up beautiful jade-9-base, 2, the 8-phenanthrene is coughed up beautiful jade-10-base, 2, the 7-phenanthrene is coughed up beautiful jade-1-base, 2, the 7-phenanthrene is coughed up beautiful jade-3-base, 2, the 7-phenanthrene is coughed up beautiful jade-4-base, 2, the 7-phenanthrene is coughed up beautiful jade-5-base, 2, the 7-phenanthrene is coughed up beautiful jade-6-base, 2, the 7-phenanthrene is coughed up beautiful jade-8-base, 2, the 7-phenanthrene is coughed up beautiful jade-9-base, 2, the 7-phenanthrene is coughed up beautiful jade-10-base, the 1-phenazinyl, the 2-phenazinyl, the 1-phenothiazinyl, the 2-phenothiazinyl, the 3-phenothiazinyl, the 4-phenothiazinyl, the lysivane base, the 1-phenoxazine group, the 2-phenoxazine group, the 3-phenoxazine group, the 4-phenoxazine group, the 10-phenoxazine group, the 2-oxazolyl, the 4-oxazolyl, the 5-oxazolyl, 2-oxadiazole base, 5-oxadiazole base, 3-furazan base, the 2-thienyl, the 3-thienyl, 2-picoline-1-base, 2-methylpyrrole-3-base, 2-methylpyrrole-4-base, 2-methylpyrrole-5-base, 3-methylpyrrole-1-base, 3-methylpyrrole-2-base, 3-methylpyrrole-4-base, 3-methylpyrrole-5-base, 2-tert-butyl group pyrroles-4-base, 3-(2-phenyl propyl) pyrroles one-1-base, 2-methyl isophthalic acid-indyl, 4-methyl isophthalic acid-indyl, 2-methyl-3-indyl, 4-methyl-3-indyl, the 2-tert-butyl group-1-indyl, the 4-tert-butyl group-1-indyl, the 2-tert-butyl group-3-indyl or the 4-tert-butyl group-3-indyl.
3. organic electronic transmission according to claim 1 and/or hole barrier materials is characterized in that: described R 2, R 2', R 5, R 5' in the fluoro methyl be-methyl that fluorine, difluoro or trifluoro replace;
Described R 2, R 2', R 5, R 5' in have 2 to 20 carbon atoms ester group be carbomethoxy, ethoxycarbonyl, propyl ester base, isopropyl ester base, positive butyl ester base, Zhong Ding ester group, isobutyl ester group, n-pentyl ester base, just own ester group, positive heptyl ester base or n-octyl base.
4. organic electronic transmission according to claim 1 and/or hole barrier materials is characterized in that: described Ar 1, Ar 1', Ar 2, Ar 2' in have 6 to 50 ring carbon atoms aryl be phenyl, the 1-naphthyl, the 2-naphthyl, the 1-anthryl, the 2-anthryl, the 9-anthryl, the 1-phenanthryl, the 2-phenanthryl, the 3-phenanthryl, the 4-phenanthryl, the 9-phenanthryl, 1-aphthacene base, 2-aphthacene base, 9-aphthacene base, the 1-pyrenyl, the 2-pyrenyl, the 4-pyrenyl, the 2-xenyl, the 3-xenyl, the 4-xenyl, para-terpheny-4-base, para-terpheny-3-base, para-terpheny-2-base, meta-terphenyl-4-base, meta-terphenyl-3-base, meta-terphenyl-2-base, o-tolyl, between tolyl, p-methylphenyl, to tert-butyl-phenyl, right-(2-phenyl propyl) phenyl, 3-methyl-2-naphthyl, 4-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-anthryl, 4 '-methyl biphenyl or 4 "-tert-butyl group-para-terpheny-4-base;
Described Ar 1, Ar 1', Ar 2, Ar 2' in have 5 to 50 annular atomses aromatic heterocyclic radical be the 1-pyrrole radicals, the 2-pyrrole radicals, the 3-pyrrole radicals, pyridine radicals, the 2-pyridine radicals, the 3-pyridine radicals, the 4-pyridine radicals, the 1-indyl, the 2-indyl, the 3-indyl, the 4-indyl, the 5-indyl, the 6-indyl, the 7-indyl, the 1-isoindolyl, the 2-isoindolyl, the 3-isoindolyl, the 4-isoindolyl, the 5-isoindolyl, the 6-isoindolyl, the 7-isoindolyl, the 2-furyl, the 3-furyl, the 2-benzofuranyl, the 3-benzofuranyl, the 4-benzofuranyl, the 5-benzofuranyl, the 6-benzofuranyl, the 7-benzofuranyl, the 1-isobenzofuran-base, the 3-isobenzofuran-base, the 4-isobenzofuran-base, the 5-isobenzofuran-base, the 6-isobenzofuran-base, the 7-isobenzofuran-base, the 2-quinolyl, the 3-quinolyl, the 4-quinolyl, the 5-quinolyl, the 6-quinolyl, the 7-quinolyl, the 8-quinolyl, the 1-isoquinolyl, the 3-isoquinolyl, the 4-isoquinolyl, the 5-isoquinolyl, the 6-isoquinolyl, the 7-isoquinolyl, the 8-isoquinolyl, the 2-quinoxalinyl, the 5-quinoxalinyl, the 6-quinoxalinyl, the 1-carbazyl, the 2-carbazyl, the 3-carbazyl, the 4-carbazyl, the 9-carbazyl, 1-coffee pyridine base, 2-coffee pyridine base, 3-coffee pyridine base, 4-coffee pyridine base, 6-coffee pyridine base, 7-coffee pyridine base, 8-coffee pyridine base, 9-coffee pyridine base, 10-coffee pyridine base, the 1-acridinyl, the 2-acridinyl, the 3-acridinyl, the 4-acridinyl, the 9-acridinyl, 1, the 7-phenanthrene is coughed up beautiful jade-2-base, 1, the 7-phenanthrene is coughed up beautiful jade-3-base, 1, the 7-phenanthrene is coughed up beautiful jade-4-base, 1, the 7-phenanthrene is coughed up beautiful jade-5-base, 1, the 7-phenanthrene is coughed up beautiful jade-6-base, 1, the 7-phenanthrene is coughed up beautiful jade-8-base, 1, the 7-phenanthrene is coughed up beautiful jade-9-base, 1, the 7-phenanthrene is coughed up beautiful jade-10-base, 1, the 8-phenanthrene is coughed up beautiful jade-2-base, 1, the 8-phenanthrene is coughed up beautiful jade-3-base, 1, the 8-phenanthrene is coughed up beautiful jade-4-base, 1, the 8-phenanthrene is coughed up beautiful jade-5-base, 1, the 8-phenanthrene is coughed up beautiful jade-6-base, 1, the 8-phenanthrene is coughed up beautiful jade-7-base, 1, the 8-phenanthrene is coughed up beautiful jade-9-base, 1, the 8-phenanthrene is coughed up beautiful jade-10-base, 1, the 9-phenanthrene is coughed up beautiful jade-2-base, 1, the 9-phenanthrene is coughed up beautiful jade-3-base, 1, the 9-phenanthrene is coughed up beautiful jade-4-base, 1, the 9-phenanthrene is coughed up beautiful jade-5-base, 1, the 9-phenanthrene is coughed up beautiful jade-6-base, 1, the 9-phenanthrene is coughed up beautiful jade-7-base, 1, the 9-phenanthrene is coughed up beautiful jade-8-base, 1, the 9-phenanthrene is coughed up beautiful jade-10-base, 1, the 10-phenanthrene is coughed up beautiful jade-2-base, 1, the 10-phenanthrene is coughed up beautiful jade-3-base, 1, the 10-phenanthrene is coughed up beautiful jade-4-base, 1, the 10-phenanthrene is coughed up beautiful jade-5-base, 2,9-phenanthrolines-1-base, 2, the 9-phenanthrene is coughed up beautiful jade-3-base, 2, the 9-phenanthrene is coughed up beautiful jade-4-base, 2, the 9-phenanthrene is coughed up beautiful jade-5-base, 2, the 9-phenanthrene is coughed up beautiful jade-6-base, 2, the 9-phenanthrene is coughed up beautiful jade-7-base, 2, the 9-phenanthrene is coughed up beautiful jade-8-base, 2, the 9-phenanthrene is coughed up beautiful jade-10-base, 2, the 8-phenanthrene is coughed up beautiful jade-1-base, 2, the 8-phenanthrene is coughed up beautiful jade-3-base, 2, the 8-phenanthrene is coughed up beautiful jade-4-base, 2, the 8-phenanthrene is coughed up beautiful jade-5-base, 2, the 8-phenanthrene is coughed up beautiful jade-6-base, 2, the 8-phenanthrene is coughed up beautiful jade-7-base, 2, the 8-phenanthrene is coughed up beautiful jade-9-base, 2, the 8-phenanthrene is coughed up beautiful jade-10-base, 2, the 7-phenanthrene is coughed up beautiful jade-1-base, 2, the 7-phenanthrene is coughed up beautiful jade-3-base, 2, the 7-phenanthrene is coughed up beautiful jade-4-base, 2, the 7-phenanthrene is coughed up beautiful jade-5-base, 2, the 7-phenanthrene is coughed up beautiful jade-6-base, 2, the 7-phenanthrene is coughed up beautiful jade-8-base, 2, the 7-phenanthrene is coughed up beautiful jade-9-base, 2, the 7-phenanthrene is coughed up beautiful jade-10-base, the 1-phenazinyl, the 2-phenazinyl, the 1-phenothiazinyl, the 2-phenothiazinyl, the 3-phenothiazinyl, the 4-phenothiazinyl, the lysivane base, the 1-phenoxazine group, the 2-phenoxazine group, the 3-phenoxazine group, the 4-phenoxazine group, the 10-phenoxazine group, the 2-oxazolyl, the 4-oxazolyl, the 5-oxazolyl, 2-oxadiazole base, 5-oxadiazole base, 3-furazan base, the 2-thienyl, the 3-thienyl, 2-picoline-1-base, 2-methylpyrrole-3-base, 2-methylpyrrole-4-base, 2-methylpyrrole-5-base, 3-methylpyrrole-1-base, 3-methylpyrrole-2-base, 3-methylpyrrole-4-base, 3-methylpyrrole-5-base, 2-tert-butyl group pyrroles-4-base, 3-(2-phenyl propyl) pyrroles-1-base, 2-methyl isophthalic acid-indyl, 4-methyl isophthalic acid-indyl, 2-methyl-3-indyl, 4-methyl-3-indyl, the 2-tert-butyl group-1-indyl, the 4-tert-butyl group-1-indyl, the 2-tert-butyl group-3-indyl or the 4-tert-butyl group-3-indyl.
5. synthetic method according to each described organic electronic transmission of claim 1～4 and/or hole barrier materials is characterized in that described synthetic method may further comprise the steps:
(1). will have substituent R 4, R 5, R 4', R 5' 2-bromo-1-acetophenone, have substituent R 5, Ar 2, R 5', Ar 2' the bromo aryl methyl ketone or have substituent R 5, Ar 2, R 5', Ar 2' bromo aromatic heterocycle ethyl ketone and pyridine raw material, be that 1: 1 ratio is dissolved in the organic solvent with mol ratio, stir, filter and obtain pyridinium tribromide salt product;
(2). under inert gas shielding, the pyridinium tribromide salt product that step (1) is obtained and has substituent R 1Dialdehyde and have a substituent R 2, R 3, R 2', R 3' acetophenone, have substituent R 2, Ar 1, R 2', Ar 1' aryl methyl ketone or have substituent R 2, Ar 1, R 2', Ar 1' the aryl-heterocyclic ethyl ketone, be 2: 1: 2 mixed with mol ratio, and be mixed with the ammonium acetate of catalytic amount, mixture is dissolved in the glacial acetic acid refluxes then, filter out product, through column chromatography chromatogram or recrystallization, obtain the polyaryl substituted pyridine derivative;
Wherein: R 1, R 2, R 2', R 3, R 3', R 4, R 4', R 5, R 5', Ar 1, Ar 1', Ar 2, Ar 2' definition with claim 1.
6. method according to claim 5 is characterized in that: described organic solvent is methyl alcohol, ethanol, oxolane, carrene or dioxane.
7. purposes according to each described organic electronic transmission of claim 1～4 and/or hole barrier materials, it is characterized in that: described organic electronic transmission and/or hole barrier materials are used to prepare organic electroluminescence device as the electron transfer layer and/or the hole barrier layer material of organic electroluminescence device.
8. purposes according to claim 7 is characterized in that: described organic electronic transmission and/or hole barrier materials are as the organic light emission layer material of organic electroluminescence device.
9. purposes according to claim 7, it is characterized in that: described organic electroluminescence device comprises negative electrode, anode and organic thin film layer, at least comprise organic luminous layer in the organic thin film layer between negative electrode and anode, and in the organic thin film layer at least one deck comprise the described polyaryl substituted pyridine derivative of claim 1.
10. according to claim 7,8 or 9 described purposes, it is characterized in that: described organic electroluminescence device can be used in organic integration circuit, organic solar batteries, organic laser or the organic sensor.
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Citations (1)

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Publication number Priority date Publication date Assignee Title
CN1954446A (en) * 2003-11-27 2007-04-25 默克专利有限公司 Organic electroluminescent element

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1954446A (en) * 2003-11-27 2007-04-25 默克专利有限公司 Organic electroluminescent element

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