CN109020971A - A kind of azepine carbazole compound and its organic luminescent device - Google Patents

A kind of azepine carbazole compound and its organic luminescent device Download PDF

Info

Publication number
CN109020971A
CN109020971A CN201810978626.8A CN201810978626A CN109020971A CN 109020971 A CN109020971 A CN 109020971A CN 201810978626 A CN201810978626 A CN 201810978626A CN 109020971 A CN109020971 A CN 109020971A
Authority
CN
China
Prior art keywords
unsubstituted
substituted
compound
carbazole compound
base
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201810978626.8A
Other languages
Chinese (zh)
Inventor
韩春雪
蔡辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun Haipurunsi Technology Co Ltd
Original Assignee
Changchun Haipurunsi Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changchun Haipurunsi Technology Co Ltd filed Critical Changchun Haipurunsi Technology Co Ltd
Priority to CN201810978626.8A priority Critical patent/CN109020971A/en
Publication of CN109020971A publication Critical patent/CN109020971A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The present invention provides a kind of azepine carbazole compound and its organic luminescent device, is related to organic optoelectronic materials technology.The present invention passes through 1,3, in 5- triazine main structure, connect substituted or unsubstituted azepine carbazolyl group, the electron transport material that the combination is formed has good electron transport ability, applied to electron transfer layer is used as in organic luminescent device, hole and electronics can be improved in the recombination rate of luminescent layer, improve the luminous efficiency of device.The combination increases conjugated system, and continuous pi-conjugated system brings preferable electron mobility, to have high electron mobility, improves carrier transmission performance, so that carrier transport balances.Such compounds process for production thereof is simple, raw material is easy to get, and is applied in OLED device as electron transfer layer, can improve the luminous efficiency of device significantly, while the driving voltage of device can also be effectively reduced, be the OLED material of a kind of function admirable.

Description

A kind of azepine carbazole compound and its organic luminescent device
Technical field
The present invention relates to organic photoelectrical material technical field more particularly to a kind of azepine carbazole compounds and its organic hair Optical device.
Background technique
The Tang etc. of Kodak Company in 1987 has invented sandwich type organic bilayer film luminescent device, this is breakthrough Progress allows it is seen that the great potential that OLED technology move towards functionization, moves towards commercial market, has started organic light-emitting diodes The research boom of pipe.Over 30 years, OLED technology achieves development with rapid changepl. never-ending changes and improvements, moves towards the industrialization life from laboratory research It produces.
Currently, the development of OLED material is to the stage of a comparative maturity, Materials Co., Ltd both domestic and external is provided Hundreds of innovative material is provided with selecting.Oled light sulfate ferroelectric functional material applied to OLED device can be divided into two from purposes Major class, i.e. charge inject transmission material and luminescent material, further, can also inject charge into transmission material and be divided into electron injection biography Transmission material is injected in defeated material and hole, and luminescent material can also be divided into main body luminescent material and dopant material.In order to make High performance OLED luminescent device, it is desirable that various organic functional materials have good photoelectric characteristic, for example, are used for organic electroluminescence The electron transport material of luminescence studies, electron transport material are organic semi-conductor important components, and in general, electronics passes Defeated material should meet following condition: 1, having good electron transport property, i.e. electron mobility is high；2, with higher Electron affinity energy is easy to inject electronics by cathode；3, relatively high ionization energy is conducive to stop hole；4, cannot with shine Layer forms exciplex；5, film forming and good thermal stability are not easy to crystallize.
All in all, the direction of the following OLED is to develop high efficiency, high brightness, the white light parts of low cost and full color to show Show device, but the technological industrialization process still faces many critical issues, how to design the better material of new performance and carry out It adjusts, is always those skilled in the art's urgent problem to be solved.
Summary of the invention
It is provided by the invention to have the object of the present invention is to provide a kind of azepine carbazole compound and its organic luminescent device Machine compound has good electronic transmission performance, and thermal stability is good, and good film-forming property, synthetic method is simple to operation, uses this There is the organic luminescent device of electron transport material preparation good luminous efficiency and service life to show.
The present invention provides a kind of azepine carbazole compounds, and general formula of molecular structure is as shown in chemical formula I:
Wherein, R1、R2Independently selected from H, cyano, substituted or unsubstituted C1~C8 alkyl, substituted or unsubstituted C6~ One of C14 aryl, substituted or unsubstituted C3~C13 heteroaryl；
Ar is selected from following group:
Wherein, X1~X4Independently selected from carbon atom or nitrogen-atoms；R3Selected from substituted or unsubstituted C1~C10 alkyl, take One of generation or unsubstituted C6~C14 aryl, substituted or unsubstituted C3~C18 heteroaryl；
L is selected from singly-bound or following group:
Wherein, R4、R5Independently selected from H, cyano, halogen atom, substituted or unsubstituted C1~C10 alkyl, replace or not One of substituted C6~C14 aryl, substituted or unsubstituted C3~C18 heteroaryl.
Preferably, Ar is selected from one of following group:
Preferably, R1、R2In at least one be cyano；
L is selected from singly-bound or following group:
Wherein, R4、R5Independently selected from one in H, methyl, ethyl, isopropyl, tert-butyl, phenyl, xenyl, naphthalene Kind.
Preferably, general formula of molecular structure is selected from one of chemical formula II, III, IV, V:
Preferably, R3Selected from methyl, ethyl, isopropyl, tert-butyl, substituted or unsubstituted phenyl, substituted or unsubstituted Naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substitution or not Substituted acridinyl, substituted or unsubstituted phenoxazine base, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazine It is thiophene base, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted Quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted purine radicals, substituted or unsubstituted indyl, take Generation or unsubstituted ferrosin base, substituted or unsubstituted base, substituted or unsubstituted acenaphthenyl, substituted or unsubstituted pyridine Base, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substitution do not take The triazine radical in generation, substituted or unsubstituted pyrrole radicals, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazole Base, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted dibenzothiophene, substitution Or one of unsubstituted dibenzofuran group.
Preferably, L is selected from singly-bound or following group:
Most preferably, any one of azepine carbazole compound of the invention in chemical structure as follows:
The present invention also provides a kind of organic luminescent device, the organic luminescent device includes cathode, anode and is placed in institute State between two electrodes and except one or more organic matter layers, the organic matter layer contains any nitrogen of the present invention Miscellaneous carbazole compound.
Preferably, organic matter layer of the present invention includes electron transfer layer, is contained in electron transfer layer of the present invention Any azepine carbazole compound.
Beneficial effects of the present invention:
The present invention provides a kind of azepine carbazole compound and its organic luminescent device, the present invention pass through in 1,3,5-triazines In main structure, substituted or unsubstituted azepine carbazolyl group is connected, on the one hand, azepine carbazole group has very high triple State energy level and stable energy level, not only remain the high triplet of carbazole group, and unsaturated C=N is also introduced into group Double bond improves electron transport ability, by the way that the tune to material carrier transmittability even may be implemented from different group keys Section；The electron transport material that the combination is formed has good electron transport ability, applied to making in organic luminescent device For electron transfer layer, hole and electronics can be improved in the recombination rate of luminescent layer, improve the luminous efficiency of device.
On the one hand, which increases conjugated system, and continuous pi-conjugated system brings preferable electron mobility, To have high electron mobility, carrier transmission performance is improved, so that carrier transport balances.
On the one hand, triazine group especially structure is more stable, acid and alkali-resistance and high temperature resistant, has high glass transition temperature；Three Piperazine group has high electron mobility and lower as typical strong electron-withdrawing group group, using it as the compound of center structure Energy level.
Azepine carbazole compound preparation method of the present invention is simple, and raw material is easy to get, and can satisfy industrialization demand.
Azepine carbazole compound of the present invention is applied in organic luminescent device, can be used as electron transfer layer, adopts There is good luminous efficiency with organic luminescent device prepared by azepine carbazole compound of the present invention and reduce device Driving voltage.
Specific embodiment:
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, art technology Personnel's every other embodiment obtained without making creative work, belongs to protection scope of the present invention.
Alkyl of the present invention refers to alkyl made of minusing a hydrogen atom in alkane molecule, can be straight chain alkane Base, branched alkyl, naphthenic base, example may include methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth Base, amyl, isopentyl, cyclopenta, cyclohexyl etc., but not limited to this.
Aryl of the present invention refers to remove a hydrogen atom on the aromatic core carbon of aromatic hydrocarbon molecule after, be left the total of univalent perssad Claiming, can be monocyclic aryl or fused ring aryl, example may include phenyl, xenyl, naphthalene, anthryl, phenanthryl or pyrenyl etc., but It is without being limited thereto.
Heteroaryl of the present invention refers to the group that one or more aromatic core carbon in aryl are substituted by hetero atom General name, the hetero atom include but is not limited to oxygen, sulphur or nitrogen-atoms, and the heteroaryl can be bicyclic heteroaryl or condensed ring heteroaryl Base, example may include pyridyl group, pyrrole radicals, pyrimidine radicals, thienyl, furyl, indyl, quinolyl, isoquinolyl, benzo thiophene Pheno base, benzofuranyl, dibenzofuran group, dibenzothiophene, carbazyl etc., but not limited to this.
Substituted alkyl of the present invention, substituted aryl, substituted heteroaryl, the substituent group is independently selected from first Base, ethyl, isopropyl, tert-butyl, phenyl, naphthalene, anthryl, phenanthryl, benzo phenanthryl, base, pyrenyl, benzyl, fluorenyl, 9,9- Dimethyl fluorenyl, hexichol amido, dimethylamino, carbazyl, 9- phenyl carbazole base, furyl, thienyl, cyano, halogen atom, Deuterium base, trifluoromethyl, phenothiazinyl, phenoxazine base, acridinyl, piperidyl, pyridyl group, pyrazinyl, triazine radical, pyrimidine radicals, connection Phenyl, terphenyl, nitro etc., but not limited to this.
The present invention provides a kind of azepine carbazole compounds, and general formula of molecular structure is as shown in chemical formula I:
Wherein, R1、R2Independently selected from H, cyano, substituted or unsubstituted C1~C8 alkyl, substituted or unsubstituted C6~ One of C14 aryl, substituted or unsubstituted C3~C13 heteroaryl；
Ar is selected from following group:
Wherein, X1~X4Independently selected from carbon atom or nitrogen-atoms；R3Selected from substituted or unsubstituted C1~C10 alkyl, take One of generation or unsubstituted C6~C14 aryl, substituted or unsubstituted C3~C18 heteroaryl；
L is selected from singly-bound or following group:
Wherein, R4、R5Independently selected from H, cyano, halogen atom, substituted or unsubstituted C1~C10 alkyl, replace or not One of substituted C6~C14 aryl, substituted or unsubstituted C3~C18 heteroaryl.
Preferably, Ar is selected from one of following group:
Preferably, R1、R2In at least one be cyano；
L is selected from singly-bound or following group:
Wherein, R4、R5Independently selected from one in H, methyl, ethyl, isopropyl, tert-butyl, phenyl, xenyl, naphthalene Kind.
Preferably, general formula of molecular structure is selected from one of chemical formula II, III, IV, V:
Preferably, R3Selected from methyl, ethyl, isopropyl, tert-butyl, substituted or unsubstituted phenyl, substituted or unsubstituted Naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substitution or not Substituted acridinyl, substituted or unsubstituted phenoxazine base, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazine It is thiophene base, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted Quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted purine radicals, substituted or unsubstituted indyl, take Generation or unsubstituted ferrosin base, substituted or unsubstituted base, substituted or unsubstituted acenaphthenyl, substituted or unsubstituted pyridine Base, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substitution do not take The triazine radical in generation, substituted or unsubstituted pyrrole radicals, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazole Base, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted dibenzothiophene, substitution Or one of unsubstituted dibenzofuran group.
Preferably, L is selected from singly-bound or following group:
Most preferably, any one of azepine carbazole compound of the invention in chemical structure as follows:
The synthesis of azepine carbazole compound of the present invention, II, III, IV, V compound of general formula of molecular structure is logical Following specific synthetic route is crossed to obtain:
Azepine carbazole compound of the invention uses popular response condition well-known to those skilled in the art.This Invention is not particularly limited the source of raw material employed in this above-mentioned all kinds of reaction, can be used commercial product raw material or The azepine carbazole compound of chemical formula I of the present invention is obtained using preparation method well-known to those skilled in the art.
The present invention limitation not special to above-mentioned reaction be using popular response well-known to those skilled in the art Can, the preparation method is simple, easily operated.
The present invention also provides a kind of organic luminescent device, the organic luminescent device includes cathode, anode and is placed in institute State between two electrodes and except one or more organic matter layers, the organic matter layer contains azepine carbazole of the present invention Class compound.
Preferably, the organic matter layer includes electron transfer layer, is contained in electron transfer layer of the present invention any Azepine carbazole compound.
OLED structure of the present invention are as follows: ITO is as transparent anode；2-TNATA is used as hole injection layer； NPB is used as hole transmission layer；CBP:Ir (ppy)3As luminescent layer；TPBi or azepine carbazole compound of the present invention are used Make electron transfer layer；LiF is used as electron injecting layer；Al is used as cathode.
Azepine carbazole compound of the present invention is used as electron transfer layer, to manufacture having for construction same as below Machine luminescent device:
ITO/2-TNATA (50nm)/NPB (30nm)/CBP:Ir (ppy)3(30nm)/electron-transport of the present invention material Expect (30nm)/LiF (0.5nm)/Al (200nm).
Organic luminescent device of the present invention can be widely applied to Display panel, lighting source, flexibility OLED, Electronic Paper, The fields such as Organophotoreceptor or Organic Thin Film Transistors, direction board, signal lamp.
The synthesis of [embodiment 1] compound 1
Step1: compound a (12.18g, 37.6mmol) is dissolved in tetrahydrofuran (140mL), is dripped under the conditions of -78 DEG C After adding hexane solvent and 2.5M n-BuLi (18mL, 45.1mmol), stir 1 hour.Trimethylborate is slowly added dropwise again After (13mL, 56.4mmol), 2h is stirred.2M hydrochloric acid is added dropwise again to neutralize, extract product with ethyl acetate and water.Use methylene chloride Compound 1-A (5.09g, 47%) is recrystallized to give with hexane.
Step2: compound b (3.42g, 13.20mmol) is dissolved completely in 50mlN, N- bis- in 250ml round-bottomed flask In methylformamide, acquired solution is then stirred at normal temperature.Into the reaction solution add malononitrile (1.05g, 15.84mmol), then acquired solution is stirred at normal temperature 1 hour.After reaction terminates, water is added thereto, and is filtered logical It crosses and acquired solution is stirred into 10 minutes sediments generated.Gained residue is diluted with ethyl acetate, is removed through anhydrous magnesium sulfate Then moisture, filtration residue are concentrated under reduced pressure.The solution silica gel column chromatography (Hex:EA=3:1) of concentration is purified to make Standby compound c (2.10g, 52%).
Step3: being added compound 1-A (28.81g, 100mmol) in reactor, compound c (30.60g, 100mmol), Tetra-triphenylphosphine palladium (1.15g, 1mmol) and sodium carbonate (41.4g, 300mmol), are dissolved in toluene for weighed reactant In (1L)/EtOH (200mL)/distilled water (200mL) solvent, 90 DEG C are heated 2 hours.The reaction mixture is cooled to room Temperature is filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and is extracted with toluene, and merges organic phase, It is evaporated under vacuum.The residue is filtered via silica gel, and is recrystallized.Obtain compound 1 (27.29g, 58%) yield is.
Mass spectrum m/z:470.16 (calculated value: 470.15).Theoretical elemental content (%) C30H18N4: C, 84.24；H, 3.86； N, 11.91 actual measurement constituent content (%): C, 84.24；H, 3.85；N, 11.92.The above results confirm to obtain product as target production Product.
The synthesis of [embodiment 2] compound 4
Weigh intermediate g (10.13g, 41mmol), compound 4-e (7.06g, 41.5mmol), cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol), and toluene is added to by said sequence In (250mL), return stirring.It vacuum distillation, methylene chloride and hexane is extracted with ethyl acetate crosses pillar and obtain compound 4-a (9.84g, 83%).
Other synthesis steps obtain compound according to Step1, Step2, Step3 synthetic method in 1 compound 1 of embodiment 4 (27.06g, 62%).
Mass spectrum m/z:436.18 (calculated value: 436.17).Theoretical elemental content (%) C30H20N4: C, 82.55；H, 4.62； N, 12.84 actual measurement constituent content (%): C, 82.55；H, 4.61；N, 12.85.The above results confirm to obtain product as target production Product.
The synthesis of [embodiment 3] compound 8
The compound 4-e in 2 compound 4 of embodiment is changed into equimolar compound 8-e, according to 2 compound 4 of embodiment Synthetic method obtain compound 8 (29.70g, 63%).
Mass spectrum m/z:471.16 (calculated value: 471.15).Theoretical elemental content (%) C32H17N5: C, 81.51；H, 3.63； N, 14.85 actual measurement constituent content (%): C, 81.50；H, 3.64；N, 14.85.The above results confirm to obtain product as target production Product.
The synthesis of [embodiment 4] compound 12
The compound 4-e in 2 compound 4 of embodiment is changed into equimolar compound 12-e, according to 2 compound of embodiment 4 synthetic method obtains compound 12 (29.67g, 57%).
Mass spectrum m/z:520.18 (calculated value: 520.17).Theoretical elemental content (%) C37H20N4: C, 85.37；H, 3.87； N, 10.76 actual measurement constituent content (%): C, 85.38；H, 3.87；N, 10.75.The above results confirm to obtain product as target production Product.
The synthesis of [embodiment 5] compound 36
The compound 4-e in 2 compound 4 of embodiment is changed into equimolar compound 36-e, according to 2 compound of embodiment 4 synthetic method obtains compound 36 (28.82g, 61%).
Mass spectrum m/z:472.15 (calculated value: 472.14).Theoretical elemental content (%) C31H16N6: C, 78.80；H, 3.41； N, 17.79 actual measurement constituent content (%): C, 78.80；H, 3.42；N, 17.78.The above results confirm to obtain product as target production Product.
The synthesis of [embodiment 6] compound 53
The compound 4-e in 2 compound 4 of embodiment is changed into equimolar compound 53-e, according to 2 compound of embodiment 4 synthetic method obtains compound 53 (33.63g, 60%).
Mass spectrum m/z:560.17 (calculated value: 560.16).Theoretical elemental content (%) C39H20N4O:C, 83.56；H, 3.60； N, 9.99；O, 2.85 actual measurement constituent content (%): C, 83.57；H, 3.60；N, 9.99；O, 2.84.The above results confirmation is produced Object is target product.
The synthesis of [embodiment 7] compound 61
Compound m (8.87g, 37.6mmol) is dissolved in tetrahydrofuran (140mL), and hexane is added dropwise under the conditions of -78 DEG C After solvent and 2.5M n-BuLi (18mL, 45.1mmol), stir 1 hour.Again slowly be added dropwise trimethylborate (13mL, After 56.4mmol), 2h is stirred.2M hydrochloric acid is added dropwise again to neutralize, extract product with ethyl acetate and water.With methylene chloride and hexane It is recrystallized to give compound n (2.93g, 47%).
Compound 61-A, compound 61 synthesis step obtain compound 61 according to the synthetic method of compound 1 (32.25g, 59%).
Mass spectrum m/z:546.19 (calculated value: 546.18).Theoretical elemental content (%) C39H22N4: C, 85.69；H, 4.06； N, 10.25 actual measurement constituent content (%): C, 85.68；H, 4.07；N, 10.25.The above results confirm to obtain product as target production Product.
The synthesis of [embodiment 8] compound 62
Isosorbide-5-Nitrae-dibromobenzene in 7 compound 61 of embodiment is changed into equimolar-two naphthalene bromide of Isosorbide-5-Nitrae, according to compound 61 Synthetic method obtain compound 62 (33.41g, 56%).
Mass spectrum m/z:596.19 (calculated value: 596.20).Theoretical elemental content (%) C43H24N4: C, 86.56；H, 4.05； N, 9.39 actual measurement constituent content (%): C, 86.56；H, 4.06；N, 9.38.The above results confirm that obtaining product is target product.
The synthesis of [embodiment 9] compound 85
Compound 1-A is obtained according to the Step1 synthetic method in 1 compound 1 of embodiment.
In 250ml round-bottomed flask by compound b (2.50g, 8.92mmol), compound p (2.46g, 10.70mmol) and Sodium ethoxide (1.82g, 26.76mmol) is dissolved completely in 30ml ethyl alcohol, is then heated and is stirred acquired solution.React end Afterwards, the residue that obtains and being concentrated under reduced pressure products therefrom is diluted with tetrahydrofuran, and with water and salt water washing.It collects Organic solvent layer removes moisture through anhydrous magnesium sulfate, then filtration residue is concentrated under reduced pressure.The solution silica gel of concentration Column chromatography (Hex:EA=1:1) is purified with prepare compound q (2.27g, 56%).
Compound 1-A (28.81g, 100mmol) is added in reactor, compound q (45.52g, 100mmol), four triphens Weighed reactant is dissolved in toluene (1L)/EtOH by base phosphine palladium (1.15g, 1mmol) and sodium carbonate (41.4g, 300mmol) In the solvent of (200mL)/distilled water (200mL), 90 DEG C are heated 2 hours.The reaction mixture is cooled to room temperature, it is dilute with toluene It releases and is filtered via diatomite.The filtrate water is diluted, and is extracted with toluene, and merges organic phase, by it in vacuum Under be evaporated.The residue is filtered via silica gel, and is recrystallized, compound 85 (34.64g, 56%) is obtained.
Mass spectrum m/z:618.14 (calculated value: 618.15).Theoretical elemental content (%) C39H18F4N4: C, 75.72；H, 2.93；F, 12.28；N, 9.06 actual measurement constituent content (%): C, 75.73；H, 2.93；F, 12.28；N, 9.05.The above results card The real product that obtains is target product.
The synthesis of [embodiment 10] compound 115
The compound p in 9 compound 85 of embodiment is changed into equimolar compound r, according to the synthesis side of compound 85 Method obtains compound 115 (34.24g, 56%).
Mass spectrum m/z:406.13 (calculated value: 406.12).Theoretical elemental content (%) C28H14N4: C, 82.74；H, 3.47； N, 13.78 actual measurement constituent content (%): C, 82.75；H, 3.46；N, 13.78.The above results confirm to obtain product as target production Product.
[comparative example 1] device prepares embodiment:
Ito glass substrate is placed in distilled water and is cleaned 2 times, it is ultrasonic washing 15 minutes, different after distilled water cleans Ultrasonic washing is later dry in order for propyl alcohol, acetone, methanol equal solvent, is transferred in plasma washing machine, by above-mentioned base Plate washs 5 minutes, is sent in evaporator.
Hole injection layer 2-TNATA/50nm is successively deposited on the ito transparent electrode having had been prepared for, vapor deposition hole passes Defeated layer NPB/30nm, vapor deposition main body CBP: doping Ir (ppy)35% mixing/30nm, then vapor deposition electron transfer layer TPBi/ 30nm, cathode LiF/0.5nm, Al/200nm.
[Application Example 1-10]
To compare the TPBi in Application Example 1 change into shown compound 1 in Application Example 1-10,4,8,12,36, 53、61、62、85、115。
Table 1 is the compound of preparation of the embodiment of the present invention and the characteristics of luminescence test for comparing luminescent device prepared by substance As a result.
The characteristics of luminescence of [table 1] luminescent device is tested
The above result shows that azepine carbazole compound of the invention is applied in organic luminescent device, especially as Electron transfer layer shows the low advantage of high-luminous-efficiency, driving voltage, is luminous organic material of good performance.
It should be pointed out that the present invention is particularly described with individual embodiments, but before not departing from the principle of the invention It puts, ordinary skill people can carry out the improvement on various forms or details to the present invention, these improvement also fall into this hair In bright protection scope.

Claims (9)

1. a kind of azepine carbazole compound, which is characterized in that general formula of molecular structure is as shown in chemical formula I:
Wherein, R1、R2Independently selected from H, cyano, substituted or unsubstituted C1~C8 alkyl, substituted or unsubstituted C6~C14 One of aryl, substituted or unsubstituted C3~C13 heteroaryl；
Ar is selected from following group:
Wherein, X1~X4Independently selected from carbon atom or nitrogen-atoms；R3Selected from substituted or unsubstituted C1~C10 alkyl, replace or One of unsubstituted C6~C14 aryl, substituted or unsubstituted C3~C18 heteroaryl；
L is selected from singly-bound or following group:
Wherein, R4、R5Independently selected from H, cyano, halogen atom, substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C14 aryl, one of substituted or unsubstituted C3~C18 heteroaryl.
2. a kind of azepine carbazole compound according to claim 1, which is characterized in that Ar in following group one Kind:
3. a kind of azepine carbazole compound according to claim 1, which is characterized in that R1、R2In at least one be cyanogen Base；
L is selected from singly-bound or following group:
Wherein, R4、R5Independently selected from one of H, methyl, ethyl, isopropyl, tert-butyl, phenyl, xenyl, naphthalene.
4. a kind of azepine carbazole compound according to claim 1, which is characterized in that general formula of molecular structure is selected from chemistry One of formula II, III, IV, V:
5. a kind of azepine carbazole compound according to claim 1, which is characterized in that R3Selected from methyl, ethyl, isopropyl Base, tert-butyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted anthryl, substitution do not take The phenanthryl in generation, substituted or unsubstituted triphenylene, substituted or unsubstituted acridinyl, substituted or unsubstituted phenoxazine base, It is substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazine thiophene base, substituted or unsubstituted fluorenyl, substituted or unsubstituted Carbazyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substitution Or it is unsubstituted purine radicals, substituted or unsubstituted indyl, substituted or unsubstituted ferrosin base, substituted or unsubstituted It is base, substituted or unsubstituted acenaphthenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted Pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazine radical, substituted or unsubstituted pyrrole radicals, substitution Or it is unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, substituted or unsubstituted thienyl, substituted or unsubstituted One of furyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group.
6. a kind of azepine carbazole compound according to claim 1, which is characterized in that L is selected from singly-bound or following group:
7. a kind of azepine carbazole compound according to claim 1, which is characterized in that be selected from chemical structure as follows In any one:
8. a kind of organic luminescent device, which is characterized in that the organic luminescent device include cathode, anode and be placed in it is described two electricity Between pole and except one or more organic matter layers, the organic matter layer contains the described in any item nitrogen of claim 1~7 Miscellaneous carbazole compound.
9. a kind of organic luminescent device according to claim 8, which is characterized in that the organic matter layer includes that electronics passes Defeated layer contains the described in any item azepine carbazole compounds of claim 1~7 in electron transfer layer.
CN201810978626.8A 2018-08-27 2018-08-27 A kind of azepine carbazole compound and its organic luminescent device Withdrawn CN109020971A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810978626.8A CN109020971A (en) 2018-08-27 2018-08-27 A kind of azepine carbazole compound and its organic luminescent device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810978626.8A CN109020971A (en) 2018-08-27 2018-08-27 A kind of azepine carbazole compound and its organic luminescent device

Publications (1)

Publication Number Publication Date
CN109020971A true CN109020971A (en) 2018-12-18

Family

ID=64624967

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810978626.8A Withdrawn CN109020971A (en) 2018-08-27 2018-08-27 A kind of azepine carbazole compound and its organic luminescent device

Country Status (1)

Country Link
CN (1) CN109020971A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109053555A (en) * 2018-09-26 2018-12-21 长春海谱润斯科技有限公司 A kind of compound and its organic luminescent device of cyano-containing structure
CN109293610A (en) * 2018-10-31 2019-02-01 长春海谱润斯科技有限公司 A kind of dibenzofuran derivative and its organic electroluminescence device
CN109336782A (en) * 2018-09-26 2019-02-15 长春海谱润斯科技有限公司 A kind of fluorene kind derivative and its organic electroluminescence device
CN111116590A (en) * 2019-12-11 2020-05-08 广州医科大学 Indole compound and application and preparation method thereof
CN111747951A (en) * 2020-05-30 2020-10-09 浙江华显光电科技有限公司 Triazine compound and organic light-emitting device thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109053555A (en) * 2018-09-26 2018-12-21 长春海谱润斯科技有限公司 A kind of compound and its organic luminescent device of cyano-containing structure
CN109336782A (en) * 2018-09-26 2019-02-15 长春海谱润斯科技有限公司 A kind of fluorene kind derivative and its organic electroluminescence device
CN109053555B (en) * 2018-09-26 2021-09-07 长春海谱润斯科技股份有限公司 Compound containing cyano structure and organic light-emitting device thereof
CN109293610A (en) * 2018-10-31 2019-02-01 长春海谱润斯科技有限公司 A kind of dibenzofuran derivative and its organic electroluminescence device
CN109293610B (en) * 2018-10-31 2021-09-07 长春海谱润斯科技股份有限公司 Dibenzofurane derivative and organic electroluminescent device thereof
CN111116590A (en) * 2019-12-11 2020-05-08 广州医科大学 Indole compound and application and preparation method thereof
CN111747951A (en) * 2020-05-30 2020-10-09 浙江华显光电科技有限公司 Triazine compound and organic light-emitting device thereof

Similar Documents

Publication Publication Date Title
CN109020971A (en) A kind of azepine carbazole compound and its organic luminescent device
KR102232993B1 (en) Organic electroluminescence element
CN111138298A (en) Nitrogen-containing compound, electronic component, and electronic device
CN109134348A (en) A kind of carbazole compound and its organic luminescent device
CN109336834A (en) A kind of aryl amine derivatives and its organic electroluminescence device
WO2021135725A1 (en) Organic compound, electronic device and electronic apparatus using same
KR20110002155A (en) New compounds and organic electronic device using the same
CN108658837A (en) A kind of organic electroluminescence device
KR20140103842A (en) Novel organic compounds for organic light-emitting diode and organic light-emitting diode including the same
CN108752261A (en) A kind of benzidine compound and its organic luminescent device
CN109293516A (en) A kind of tri-arylamine group compound and its organic luminescent device
CN109467511A (en) A kind of aromatic amine compounds and its organic luminescent device
CN109232376A (en) A kind of fluorene derivative and its organic electroluminescence device
CN109096268A (en) A kind of organic electroluminescent compounds and its organic electroluminescence device
CN109360905A (en) A kind of organic electroluminescence device
CN109134369A (en) A kind of Acridine derivatives and its organic luminescent device
CN109180526A (en) A kind of anthracene derivative and its organic luminescent device
CN113135928A (en) Organic compound and organic electroluminescent device comprising same
CN109020970A (en) A kind of electron transport material and its organic luminescent device
CN108899431A (en) A kind of organic luminescent device
CN108822155A (en) It is a kind of miscellaneous with iridium complex and its organic luminescent device
CN108822154A (en) A kind of complex of iridium and its organic luminescent device
CN108774266A (en) A kind of complex of iridium and its organic luminescent device
CN108864195A (en) A kind of metal iridium complex and its organic luminescent device
CN109053555B (en) Compound containing cyano structure and organic light-emitting device thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20181218

WW01 Invention patent application withdrawn after publication