CN104672230B - Fluorene kind derivative containing aryl amine and its applied in electroluminescent device - Google Patents
Fluorene kind derivative containing aryl amine and its applied in electroluminescent device Download PDFInfo
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Abstract
The invention provides a kind of fluorene kind derivative containing aryl amine, with such as formula（1）Shown structure, wherein：Ar is selected from fluorenylidene or sub- indeno fluorenyl；R1And R2One of the aliphatic cycloalkyl of aliphatic alkyl, C1 12 independently selected from H, C1 12, C6 30 aryl, C6 30 heterocyclic aryl, triarylamine；Ar1And Ar2It is respectively and independently selected from the aryl of C1 12 aliphatic alkyl, C1 12 aliphatic cycloalkyl or C6 30；L1And L2It is respectively and independently selected from singly-bound, C1 20 alkylidene, substituted or unsubstituted C6 30 arlydene and substituted or unsubstituted C6 30 heteroarylidene；On condition that R1And R2It is asynchronously H.Such compound property is stable, and preparation technology is simple, when being used as phosphorescent light body material in electroluminescent device, and device shows higher luminous efficiency and relatively low opens bright voltage.
Description
Technical field
The present invention relates to a kind of novel organic compound, and its application in ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technology
Electroluminescent material and device pass through years of researches and development, have reached practical level, various materials,
Such as hole material, electronic material, luminescent material, display device technology of preparing has been achieved for considerable progress.With research
Work deeply and it is practical during requirement to material, it is increasingly obvious as the advantage of luminescent material with phosphorescence.Phosphorescence material
The luminous efficiency of material is higher than 3 to 4 times of fluorescent material, for many display products for requiring that brightness is higher, is with phosphor material
Primary selection.Phosphorescence luminescent layer in device is steamed altogether by two class materials to be formed, and a class is material of main part, accounts for the 90% of common steaming component
Left and right, another kind of is phosphorescent coloring, accounts for 10% or so of common steaming component.What tradition was used is 4 in phosphorescent light body material, 4 '-N,
The carbazole biphenyls of N '-two.The material has higher triplet, can be well matched with phosphorescent coloring, but due to the material point
Son measures smaller (molecular weight 484) so that glass transition temperature is relatively low (Tg about 1100C or once), is easily being crystallized using process, shape
Into island, cause not bright spot, device lifetime shortens.R and D to new phosphorescent light body material are operated in continuous progress, its
In have research patent (application number 200680047266.5, publication number that pyridine radicals is introduced into material structure
CN101331626A), also there are research patent (application number 200580014777.2, disclosure that pyrimidine radicals is introduced into material structure
Number CN 1951155A), preferable improvement effect is all obtained in various degree.
Therefore, based on existing research, the phosphorescent light body material of stability and high efficiency is further developed, so as to reduce bright electricity
Pressure, improves device efficiency, with critically important actual application value.
The content of the invention
The purpose of the present invention is to propose to a kind of new compound, such compound can be used for ORGANIC ELECTROLUMINESCENCE DISPLAYS neck
It is used as phosphorescent light body material in domain, the organic luminescence function layer in organic electroluminescent device, and then it is low to obtain driving voltage, electricity
Flow efficiency high, half-life period longer organic electroluminescence device.
In order to solve the above technical problems, the technical solution adopted in the present invention is as follows：
The phosphorescent light body material containing imidazo [1,2, a] pyridine groups and triarylamine that the present invention is provided, there is higher
Molecular weight, be conducive to the raising of glass transition temperature, meanwhile, imidazo [1,2, a] pyridine groups and carbazole group pass through sub- fluorenes
The fused ring aryl groups such as base, sub- indenes And fluorenyls are connected, and each substituent in the compound is in on-plane surface state so that whole
Molecule forms distortion to a certain extent on space multistory, and the stereoeffect of molecule is irregular, advantageously forms without fixed
Type film, particularly on the basis of triarylamine presence, present invention introduces imidazo [1,2, a] pyridine groups, is effectively adjusted
The triplet of material (T1).When the material of the present invention is used for into electroluminescent device as phosphorescence host, electricity
Photoluminescence improves significantly opening the everyways such as bright voltage, brightness, service life.
Therefore, the invention provides a kind of fluorene kind derivative containing aryl amine of the structure with as shown in formula (1)：
Wherein：
Ar is selected from fluorenylidene or sub- indeno fluorenyl；
R1And R2Separately selected from H, substituted or unsubstituted aliphatic alkyl, the carbon atom that carbon number is 1-12
Substituted or unsubstituted aryl that substituted or unsubstituted aliphatic cycloalkyl that number is 1-12, carbon number are 6-30, carbon are former
Subnumber is one of 6-30 substituted or unsubstituted heterocyclic aryl, triarylamine；Ar1And Ar2It is respectively and independently selected from carbon atom
The substituted or unsubstituted aliphatic cycloalkyl that substituted or unsubstituted aliphatic alkyl, the carbon number that number is 1-12 are 1-12
Or the substituted or unsubstituted aryl that carbon number is 6-30；
L1And L2It is respectively and independently selected from substitution that alkylidene, carbon number that singly-bound, carbon number are 1-20 are 6-30 or not
Substituted arlydene or the substituted or unsubstituted heteroarylidene that carbon number is 6-30；
On condition that R1And R2It is asynchronously H.
Further, structure shown in formula (4) can be connected directly with imidazo [1,2, a] pyridine groups, or, work as R1Or
R2During for H, structure shown in formula (4) passes through R1Or R2It is connected with imidazo [1,2, a] pyridine groups, is also just to succeed in reaching an agreement formula (4) institute
Show that structure is connected directly between R1Or R2Position on；
Further, the R1And R2Separately selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, just oneself
One of base, phenyl, tolyl, ethylbenzene, xenyl, naphthyl, naphthylphenyl, triarylamine.
In formula (1), Ar skeleton structure is selected from following structures：
Further, the Ar1And Ar2Separately it is selected from phenyl, the alkyl-substituted phenyl of C1-10, xenyl, C1-
One of 10 alkyl-substituted xenyls, naphthyl, the alkyl-substituted naphthyls of C1-10, naphthylphenyl, triarylamine.
Further, the bridge linkage group L1And L2It is independently selected from singly-bound, phenylene, biphenylene, naphthylene, sub- pyridine
One of base.
Further, R is worked as1Or R2When being not H, the R1Or R2Selected from following structures：
In order to become apparent from illustrating present invention, the narration of lower mask body the present invention relates to compound preferred structure：
The invention provides a kind of fluorene kind derivative containing aryl amine that can be applied in organic electroluminescence device.
Further, the fluorene kind derivative containing aryl amine can be used as phosphorescence host in organic electroluminescence device
Material.
Present invention also offers a kind of organic electroluminescence device, including substrate, and sequentially form on the substrate
Anode layer, organic luminescence function layer and cathode layer；Described organic luminescence function layer includes hole transmission layer, organic luminous layer
And electron transfer layer, the material of main part of the organic luminous layer is the derivative of the fluorenes class containing aryl amine described in one or more
Thing.
Further, in organic electroluminescence device, the luminescent layer is made up of material of main part and luminescent dye, described
Luminescent dye is phosphorescent coloring.
The fluorene kind derivative containing aryl amine that the present invention is developed, preparation technology is simple, easy and the material has well
Heat endurance, have the molecular orbit matched with phosphorescent coloring and triplet (T1), in organic electroluminescence device
It is good phosphorescent light body material.
Brief description of the drawings
In order that present disclosure is more easily understood, below according to specific embodiment of the invention and with reference to accompanying drawing,
The present invention is further detailed explanation；Try to achieve the highest occupied molecular of compound respectively with Gaussian 03/6-31 methods
Track (HOMO), lowest unoccupied molecular orbital (LUMO) and triplet (T1).Wherein：
Fig. 1 is the highest occupied molecular orbital(HOMO) of organic compound 12 of the present invention, and HOMO energy levels are -4.773.ev,
Triplet T1=2.2819ev；
Fig. 2 is the lowest unoccupied molecular orbital of organic compound 12 of the present invention, and lumo energy is -1.477ev.
Specific embodiment
Pyridine derivate used, phenyl-bromide are for aldehyde ketone, aryl boric acid derivative, carbazyl boronic acid derivatives in the present invention
Chemical products it can be commercially available at home Deng basic chemical industry raw material, various condensed-nuclei aromatics bromo-derivatives, condensed-nuclei aromatics boric acid derive
Thing can use common organic procedures to synthesize.
The synthesis of various intermediates
The synthesis of intermediate 1
2- amino -5- bromopyridines 0.892g (5mmol), the 1.7g bromo- 2- phenyl benzene of 2- are added in the flask of a 50ml
Ethyl ketone (6mmol), sodium acid carbonate 0.491g (6mmol), isopropanol 15ml, return stirring 12hrs, is evaporated off isopropanol, adds
30ml isopropanols and 60ml dichloromethane, collect organic phase, use pillar layer separation product, petroleum ether and ethyl acetate elution, 3：1
Proportioning.Obtain 1.17g, 67% yield.
The synthesis of intermediate 2
2- amino -4- bromopyridines 0.892g (5mmol), the 1.7g bromo- 2- phenyl benzene of 2- are added in the flask of a 50ml
Ethyl ketone (6mmol), sodium acid carbonate 0.491g (6mmol), isopropanol 15ml, return stirring 12hrs, is evaporated off isopropanol, adds
30ml isopropanols and 60ml dichloromethane, collect organic phase, use pillar layer separation product, petroleum ether and ethyl acetate elution, 3：1
Proportioning.Obtain 1.25g, 71.84% yield.
The synthesis of intermediate 3
PA 0.471g (5mmol), the 2.13g bromo- 2- of 2- (4- bromophenyls) are added in the flask of a 50ml
Acetophenone (6mmol), sodium acid carbonate 0.491g (6mmol), isopropanol 15ml, return stirring 12hrs, is evaporated off isopropanol, adds
30ml isopropanols and 60ml dichloromethane, collect organic phase, use pillar layer separation product, petroleum ether and ethyl acetate elution, 3：1
Proportioning.Obtain 1.31g, 75.3% yield.
The synthesis of intermediate 4
PA 0.471g (5mmol), 2.13g bromo- 2- phenyl (the 4- bromobenzenes of 2- are added in the flask of a 50ml
Base) ethyl ketone (6mmol), sodium acid carbonate 0.491g (6mmol), isopropanol 15ml, return stirring 12hrs are evaporated off isopropanol, added
30ml isopropanols and 60ml dichloromethane, collect organic phase, use pillar layer separation product, petroleum ether and ethyl acetate elution, 3：1
Proportioning.Obtain 1.20g, 69% yield.
The synthesis of various intermediate boric acid (by taking intermediate 1 as an example, remaining is similar)
In one 500 milliliters of there-necked flasks, with magnetic agitation, Ar gas shieldeds add 14.9g 2,3- diphenyl -6- bromine imidazoles
And [1,2, a] pyridine (molecular weight 348,0.0428mol) and 120ml THF, it is cooled to -78 DEG C, 25ml 2M nBuLi is added dropwise
(0.05mol), temperature maintains the B (OiPr) 3 that 30ml is added dropwise after -78 DEG C, stirring 10min at -78 DEG C always
(0.153mol), stirs and dilute acid hydrolysis is added to room temperature, and upper strata is white solid.Filtering, separates solid product, water layer is neutralized to
Neutrality, is extracted with ethyl acetate, and extract solution is evaporated, and adds diluted alkaline, and the not molten impurity in alkali is withdrawn with ethyl acetate, and water layer is neutralized
To neutral, there is white solid precipitation, filter, obtain product.It there are 11.7g solid products, molecular weight 314, yield 86.46%.
Embodiment 1
The synthesis of compound 1
The first step,
In one 500 milliliters of there-necked flasks, with electric stirring, Ar gas shieldeds, add 16.9g diphenylamines (molecular weight 169,
0.10mol), iodo- 9, the 9- dimethyl fluorenes 44g of the bromo- 7- of 2- (molecular weight 398,0.11mol), copper powder 15g (molecular weight 64,
0.234mol), potassium carbonate 41.4g (molecular weight 138,0.3mol), the 6.13g (molecular weight 264,0.023mol) of 18- crown-s 6, plus
Enter the common 300ml of solvent o-dichlorohenzene.Return stirring 4 hours, is monitored with TLC and reacted.After reaction completely, stir naturally to room temperature,
Solvent is evaporated off.Solid mixture is separated with silica gel column chromatography, obtains slightly yellow monobromo intermediate 40.3g, molecular weight 439, purity
97.5%, yield 89.4%.
Second step,
1000 milliliters of there-necked flasks, with magnetic agitation, add 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid 9.42g
The monobromo intermediate 12.3g (molecular weight 437,0.028mol) obtained in (molecular weight 314,0.03mol), the first step, Pd
(PPh3) 4 usage amount 1.8g (molecular weight 1154,0.00155mol), sodium carbonate 175ml (2M), toluene 175ml, ethanol 175ml.
After argon gas displacement, backflow is monitored with TLC and reacted, and reacts complete after 4 hours, and cooling separates organic layer, is evaporated, with 1/10 second
Acetoacetic ester/petroleum ether carries out post separation, obtains 14.31g compound 1, molecular weight 627, purity 98.5%, yield 74.5%.
Product MS (m/e)：629, elementary analysis (C46H35N3)：Theoretical value C：87.73%, H：5.60%, N：6.67%；Measured value C：
87.75%, H：5.62%, N：6.63%.
Embodiment 2
The synthesis of compound 2
Building-up process is allocated as two steps.First step reaction is same as the first step of embodiment 1, replaces diphenylamines to make with 1- naphtyl phenyl amines
Raw material, other reagents and process are constant, obtain corresponding monobromo intermediate；Second step reaction is same as the second step of embodiment 1, uses this
In the monobromo intermediate that synthesizes of the first step replace monobromo intermediate in embodiment 1, other reagents and process be constant, obtains chemical combination
Thing 2.
Product MS (m/e)：679, elementary analysis (C50H37N3)：Theoretical value C：88.33%, H：5.49%, N：6.18%；It is real
Measured value C：88.30%, H：5.48%, N：6.22%.
Embodiment 3
The synthesis of compound 3
Building-up process is allocated as two steps.First step reaction is same as the first step of embodiment 1, obtains corresponding monobromo intermediate；The
The reaction of two steps is same as the step of embodiment 1 the 2nd, and the monobromo intermediate synthesized with the first step replaces the monobromo intermediate in embodiment 1, uses
Simultaneously [1,2, a] pyridine -7- boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid to 2,3- diphenyl-imidazoles, other
Reagent and process are constant, obtain compound 3.Product MS (m/e)：629, elementary analysis (C46H35N3)：Theoretical value C：87.73%,
H：5.60%, N：6.67%；Measured value C：87.70%, H：5.61%, N：6.69%.
Embodiment 4
The synthesis of compound 4
Building-up process is allocated as two steps.First step reaction is same as the first step of embodiment 1, replaces diphenylamines to make with 1- naphtyl phenyl amines
Raw material, other reagents and process are constant, obtain corresponding monobromo intermediate；Second step reaction is same as the second step of embodiment 1, with the
The monobromo intermediate of one-step synthesis replace embodiment 1 in monobromo intermediate, with 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine-
7- boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid, and other reagents and process are constant, obtain compound 4.
Product MS (m/e)：679, elementary analysis (C50H37N3)：Theoretical value C：88.33%, H：5.49%, N：6.18%；It is real
Measured value C：88.31%, H：5.46%, N：6.23%.
Embodiment 5
The synthesis of compound 5
Building-up process is allocated as two steps.First step reaction is same as the first step of embodiment 1, obtains corresponding monobromo intermediate；The
The reaction of two steps is same as the second step of embodiment 1, and the monobromo intermediate synthesized with the first step replaces the monobromo intermediate in embodiment 1,
2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boron is replaced with 4- (3- phenylimidazoles simultaneously [1,2, a] pyridine -2- bases) phenyl boric acid
Acid, other reagents and process are constant, obtain compound 5.
Product MS (m/e)：629, elementary analysis (C46H35N3)：Theoretical value C：87.73%, H：5.60%, N：6.67%；
Measured value C：87.75%, H：5.61%, N：6.64%.Embodiment 6
The synthesis of compound 6
Building-up process is allocated as two steps.First step reaction is same as the first step of embodiment 1, replaces diphenylamines to make with 1- naphtyl phenyl amines
Raw material, other reagents and process are constant, obtain corresponding monobromo intermediate；Second step reaction is same as the second step of embodiment 1, with the
The monobromo intermediate of one-step synthesis replaces the monobromo intermediate in embodiment 1, with 4- (3- phenylimidazoles simultaneously [1,2, a] pyridine -2-
Base) phenyl boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid, and other reagents and process are constant, obtain compound
6。
Product MS (m/e)：679, elementary analysis (C50H37N3)：Theoretical value C：88.33%, H：5.49%, N：6.18%；It is real
Measured value C：88.34%, H：5.45%, N：6.21%.
Embodiment 7
The synthesis of compound 7
Building-up process is allocated as two steps.First step reaction is same as the first step of embodiment 1, obtains corresponding monobromo intermediate；The
The reaction of two steps is same as the second step of embodiment 1, and the monobromo intermediate synthesized with the first step replaces the monobromo intermediate in embodiment 1,
2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boron is replaced with 4- (2- phenylimidazoles simultaneously [1,2, a] pyridin-3-yl) phenyl boric acid
Acid, other reagents and process are constant, obtain compound 7.
Product MS (m/e)：629, elementary analysis (C46H35N3)：Theoretical value C：87.73%, H：5.60%, N：6.67%；It is real
Measured value C：87.74%, H：5.63%, N：6.63%.
Embodiment 8
The synthesis of compound 8
Building-up process is allocated as two steps.First step reaction is same as the first step of embodiment 1, replaces diphenylamines to make with 1- naphtyl phenyl amines
Raw material, other reagents and process are constant, obtain corresponding monobromo intermediate；Second step reaction is same as the second step of embodiment 1, with the
The monobromo intermediate of one-step synthesis replaces the monobromo intermediate in embodiment 1, with 4- (2- phenylimidazoles simultaneously [1,2, a] pyridine -3-
Base) phenyl boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid, and other reagents and process are constant, obtain compound
8。
Product MS (m/e)：679, elementary analysis (C50H37N3)：Theoretical value C：88.33%, H：5.49%, N：6.18%；It is real
Measured value C：88.36%, H：5.50%, N：6.14%.
Embodiment 9
The synthesis of compound 9
Building-up process is allocated as two steps.First step reaction is same as the first step of embodiment 1, obtains corresponding monobromo intermediate；The
The reaction of two steps is same as the second step of embodiment 1, and the monobromo intermediate synthesized with the first step replaces the monobromo intermediate in embodiment 1,
Other reagents and process are constant, obtain compound 9.
Product MS (m/e)：745, elementary analysis (C55H43N3)：Theoretical value C：88.56%, H：5.81%, N：5.63%；It is real
Measured value C：88.58%, H：5.83%, N：5.59%.
Embodiment 10
The synthesis of compound 10
Building-up process is allocated as two steps.First step reaction is same as the first step of embodiment 1, replaces diphenylamines to make with 1- naphtyl phenyl amines
Raw material, other reagents and process are constant, obtain corresponding monobromo intermediate；Second step reaction is same as the second step of embodiment 1, with the
The monobromo intermediate of one-step synthesis replaces the monobromo intermediate in embodiment 1, and other reagents and process are constant, obtain compound
10。
Product MS (m/e)：795, elementary analysis (C59H45N3)：Theoretical value C：89.02%, H：5.70%, N：5.28%；It is real
Measured value C：89.06%, H：5.71%, N：5.23%.
Embodiment 11
The synthesis of compound 11
Building-up process is allocated as two steps.First step reaction is same as the first step of embodiment 1, obtains corresponding monobromo intermediate；The
The reaction of two steps is same as the second step of embodiment 1, and the monobromo intermediate synthesized with the first step replaces the monobromo intermediate in embodiment 1,
With 2,3- diphenyl-imidazoles, simultaneously [1,2, a] pyridine -7- boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid, its
Its reagent and process are constant, obtain compound 11.Product MS (m/e)：745, elementary analysis (C55H43N3)：Theoretical value C：
88.56%, H：5.81%, N：5.63%；Measured value C：88.53%, H：5.80%, N：5.67%.
Embodiment 12
The synthesis of compound 12
Building-up process is allocated as two steps.First step reaction is same as the first step of embodiment 1, replaces diphenylamines to make with 1- naphtyl phenyl amines
Raw material, other reagents and process are constant, obtain corresponding monobromo intermediate；Second step reaction is same as the second step of embodiment 1, with the
The monobromo intermediate of one-step synthesis replace embodiment 1 in monobromo intermediate, with 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine-
7- boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid, and other reagents and process are constant, obtain compound 12.
Product MS (m/e)：795, elementary analysis (C59H45N3)：Theoretical value C：89.02%, H：5.70%, N：5.28%；It is real
Measured value C：89.00%, H：5.64%, N：5.36%.
Embodiment 13
The synthesis of compound 13
Building-up process is allocated as two steps.First step reaction is same as the first step of embodiment 1, obtains corresponding monobromo intermediate；The
The reaction of two steps is same as the second step of embodiment 1, and the monobromo intermediate synthesized with the first step replaces the monobromo intermediate in embodiment 1,
2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boron is replaced with 4- (3- phenylimidazoles simultaneously [1,2, a] pyridine -2- bases) phenyl boric acid
Acid, other reagents and process are constant, obtain compound 13.
Product MS (m/e)：745, elementary analysis (C55H43N3)：Theoretical value C：88.56%, H：5.81%, N：5.63%；It is real
Measured value C：88.52%, H：5.80%, N：5.68%.
Embodiment 14
The synthesis of compound 14
Building-up process is allocated as two steps.First step reaction is same as the first step of embodiment 1, replaces diphenylamines to make with 1- naphtyl phenyl amines
Raw material, other reagents and process are constant, obtain corresponding monobromo intermediate；Second step reaction is same as the second step of embodiment 1, with the
The monobromo intermediate of one-step synthesis replaces the monobromo intermediate in embodiment 1, with 4- (3- phenylimidazoles simultaneously [1,2, a] pyridine -2-
Base) phenyl boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid, and other reagents and process are constant, obtain compound
14。
Product MS (m/e)：795, elementary analysis (C59H45N3)：Theoretical value C：89.02%, H：5.70%, N：5.28%；It is real
Measured value C：89.05%, H：5.68%, N：5.27%.
Embodiment 15
The synthesis of compound 15
Building-up process is allocated as two steps.First step reaction is same as the first step of embodiment 1, obtains corresponding monobromo intermediate；The
The reaction of two steps is same as the second step of embodiment 1, and the monobromo intermediate synthesized with the first step replaces the monobromo intermediate in embodiment 1,
2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boron is replaced with 4- (2- phenylimidazoles simultaneously [1,2, a] pyridin-3-yl) phenyl boric acid
Acid, other reagents and process are constant, obtain compound 15.
Product MS (m/e)：745, elementary analysis (C55H43N3)：Theoretical value C：88.56%, H：5.81%, N：5.63%；It is real
Measured value C：88.58%, H：5.83%, N：5.59%.
Embodiment 16
The synthesis of compound 16
Building-up process is allocated as two steps.First step reaction is same as the first step of embodiment 1, replaces diphenylamines to make with 1- naphtyl phenyl amines
Raw material, other reagents and process are constant, obtain corresponding monobromo intermediate；Second step reaction is same as the second step of embodiment 1, with the
The monobromo intermediate of one-step synthesis replaces the monobromo intermediate in embodiment 1, with 4- (2- phenylimidazoles simultaneously [1,2, a] pyridine -3-
Base) phenyl boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid, and other reagents and process are constant, obtain compound
16。
Product MS (m/e)：795, elementary analysis (C59H45N3)：Theoretical value C：89.02%, H：5.70%, N：5.28%；It is real
Measured value C：89.01%, H：5.69%, N：5.30%.
Embodiment 17
The synthesis of compound 17
Building-up process is allocated as two steps.First step reaction is same as the second step of embodiment 1, with the iodo- tetramethyl indenos of the bromo- 7- of 2-
[3,2, b] fluorenes replace iodo- 9, the 9- dimethyl fluorenes of the bromo- 7- of 2-, replaced with triphenylamine -4- boric acid 2,3- diphenyl-imidazoles simultaneously [1,2,
A] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtain corresponding monobromo intermediate；Second step reaction is same as reality
The second step of example 1 is applied, the monobromo intermediate synthesized with the first step replaces the monobromo intermediate in embodiment 1, other reagents and process
It is constant, obtain compound 17.
Product MS (m/e)：821, elementary analysis (C61H47N3)：Theoretical value C：89.13%, H：5.76%, N：5.11%；It is real
Measured value C：89.15%, H：5.73%, N：5.12%.
Embodiment 18
The synthesis of compound 18
Building-up process is allocated as two steps.First step reaction is same as the second step of embodiment 1, with the iodo- tetramethyl indenos of the bromo- 7- of 2-
[3,2, b] fluorenes replace iodo- 9, the 9- dimethyl fluorenes of the bromo- 7- of 2-, replaced with triphenylamine -4- boric acid 2,3- diphenyl-imidazoles simultaneously [1,2,
A] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtain corresponding monobromo intermediate；Second step reaction is same as reality
The second step of example 1 is applied, the monobromo intermediate synthesized with the first step replaces the monobromo intermediate in embodiment 1, with 2,3- diphenyl miaows
Simultaneously [1,2, a] pyridine -7- boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid to azoles, and other reagents and process are not
Become, obtain compound 18.
Product MS (m/e)：821, elementary analysis (C61H47N3)：Theoretical value C：89.13%, H：5.76%, N：5.11%；It is real
Measured value C：89.11%, H：5.74%, N：5.15%.
Embodiment 19
The synthesis of compound 19
Building-up process is allocated as two steps.First step reaction is same as the second step of embodiment 1, with the iodo- tetramethyl indenos of the bromo- 7- of 2-
[3,2, b] fluorenes replace iodo- 9, the 9- dimethyl fluorenes of the bromo- 7- of 2-, replaced with triphenylamine -4- boric acid 2,3- diphenyl-imidazoles simultaneously [1,2,
A] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtain corresponding monobromo intermediate；Second step reaction is same as reality
The second step of example 1 is applied, the monobromo intermediate synthesized with the first step replaces the monobromo intermediate in embodiment 1, with 4- (3- phenylimidazoles
And [1,2, a] pyridine -2- bases) phenyl boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid, other reagents and mistake
Journey is constant, obtains compound 19.
Product MS (m/e)：821, elementary analysis (C61H47N3)：Theoretical value C：89.13%, H：5.76%, N：5.11%；It is real
Measured value C：89.10%, H：5.72%, N：5.18%.
Embodiment 20
The synthesis of compound 20
Building-up process is allocated as two steps.First step reaction is same as the second step of embodiment 1, with the iodo- tetramethyl indenos of the bromo- 7- of 2-
[3,2, b] fluorenes replace iodo- 9, the 9- dimethyl fluorenes of the bromo- 7- of 2-, replaced with triphenylamine -4- boric acid 2,3- diphenyl-imidazoles simultaneously [1,2,
A] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtain corresponding monobromo intermediate；Second step reaction is same as reality
The second step of example 1 is applied, the monobromo intermediate synthesized with the first step replaces the monobromo intermediate in embodiment 1, with 4- (3- phenylimidazoles
And [1,2, a] pyridine -2- bases) phenyl boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid, other reagents and mistake
Journey is constant, obtains compound 20.
Product MS (m/e)：821, elementary analysis (C61H47N3)：Theoretical value C：89.13%, H：5.76%, N：5.11%；It is real
Measured value C：89.16%, H：5.77%, N：5.07%.
Embodiment 21
The synthesis of compound 21
Building-up process is allocated as two steps.First step reaction is same as the second step of embodiment 1, with the iodo- tetramethyl indenos of the bromo- 7- of 2-
[3,2, b] fluorenes replaces iodo- 9, the 9- dimethyl fluorenes of the bromo- 7- of 2-, and 2,3- diphenyl is replaced with 4 ', 4 '-dimethyltrianiline -4- boric acid
Imidazo [1,2, a] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtains corresponding monobromo intermediate；Second step
Reaction is same as the second step of embodiment 1, and the monobromo intermediate synthesized with the first step replaces the monobromo intermediate in embodiment 1, uses 4-
(3- phenylimidazoles simultaneously [1,2, a] pyridine -2- bases) phenyl boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid, its
Its reagent and process are constant, obtain compound 21.
Product MS (m/e)：849, elementary analysis (C63H51N3)：Theoretical value C：89.01%, H：6.05%, N：4.94%；It is real
Measured value C：89.03%, H：6.07%, N：4.90%.
Embodiment 22
The synthesis of compound 22
Building-up process is allocated as two steps.First step reaction is same as the second step of embodiment 1, with the iodo- tetramethyl indenos of the bromo- 7- of 2-
[3,2, b] fluorenes replaces iodo- 9, the 9- dimethyl fluorenes of the bromo- 7- of 2-, and 2,3- diphenyl is replaced with 4 ', 4 '-dimethyltrianiline -4- boric acid
Imidazo [1,2, a] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtains corresponding monobromo intermediate；Second step
Reaction is same as the second step of embodiment 1, and the monobromo intermediate synthesized with the first step replaces the monobromo intermediate in embodiment 1, uses 4-
(2- phenylimidazoles simultaneously [1,2, a] pyridin-3-yl) phenyl boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid, its
Its reagent and process are constant, obtain compound 22.
Product MS (m/e)：849, elementary analysis (C63H51N3)：Theoretical value C：89.01%, H：6.05%, N：4.94%；It is real
Measured value C：89.02%, H：6.03%, N：4.95%.Here is the Application Example of the compounds of this invention：
Embodiment 23：The preparation of electroluminescent device and result
Prepare the preferred embodiment of device：
(1) device is designed
Compare the performance of these materials for convenience, the present invention devise a simple electroluminescent device (substrate/anode/
Hole transmission layer (HTL)/phosphorescent coloring/phosphorescence host (EL)/electron transfer layer (ETL)/negative electrode), using only compound 1,4,
5th, 8,10,13,15,18,22 as phosphorescent light body material illustration, and CBP or NPB or mCP compare material, Ir as phosphorescence host
(ppy)3、Ir(piq)3With Firpic respectively as phosphorescent coloring.The structure of CBP and phosphorescent coloring is：
Substrate can use the substrate in conventional organic luminescence device, for example：Glass or plastics.In the device system of the present invention
Glass substrate is selected in work, ITO makees anode material.
Hole transmission layer can use various tri-arylamine group materials.Selected hole is passed in the element manufacturing of the present invention
Defeated material is NPB.
Selected electron transport material is Bphen in the element manufacturing of the present invention.
Negative electrode can use metal and its mixture structure, such as Mg：Ag、Ca：Ag etc. or electron injecting layer/gold
Belong to Rotating fields, such as LiF/Al, Li2O/Al common cathode structure.The selected electron injection in the element manufacturing of the present invention
Material is LiF, and cathode material is Al.
(2) element manufacturing
The glass plate of transparent conductive layer will be coated with ultrasonically treated in commercial detergent, rinsed in deionized water,
In acetone：Ultrasonic oil removing in alcohol mixed solvent, is baked under clean environment and removes moisture content completely, clear with ultraviolet light and ozone
Wash, and with low energy cation beam bombarded surface；The above-mentioned glass substrate with anode is placed in vacuum chamber, it is evacuated to 1 ×
10-5~9 × 10-3Pa, vacuum evaporation NPB is as hole transmission layer on above-mentioned anode tunic, and evaporation rate is 0.1nm/s, steams
Plating thickness is 40nm；
The phosphorescent light body material 1,4,5,8,10,13,15,18,22 of the vacuum evaporation present invention on hole transmission layer, together
When phosphorescent coloring Ir (ppy) is deposited altogether3(or FIrpic, or Ir (piq)3), phosphorescent light body material can also use CBP or NPB or mCP
Instead of.The luminescent layer as device is deposited in phosphorescence host and dyestuff altogether, and evaporation rate is 0.1nm/s, and evaporation total film thickness is 30nm,
Luminescent dye Ir (ppy)3Doping concentration be 10%, FIrpic doping concentration be 12%, Ir (piq)3Doping concentration be
5%, doping concentration mentioned here refers to that the evaporation rate ratio of luminescent dye and material of main part is 10:100,12:100,5:
100；
The stratification compound Bphen of vacuum evaporation one is as the electron transfer layer of device on luminescent layer, and its evaporation rate is
0.1nm/s, evaporation total film thickness is 20nm；
Vacuum evaporation LiF is used as electron injecting layer, thickness 0.5nm on electron transfer layer (ETL).Steamed on LiF layers
The Al layers of negative electrode as device is plated, thickness is 150nm.
Device performance see the table below (device architecture：ITO/NPB (40nm)/phosphorescent coloring/phosphorescence host (30nm)/Bphen
(20nm)/LiF(0.5nm)/Al(150nm))
Result above shows that new organic materials of the invention are used for organic electroluminescence device, can effectively reduce
Landing voltage, improves current efficiency, is phosphorescence host of good performance.
Although the present invention is described in conjunction with the embodiments, the invention is not limited in above-described embodiment, it should manage
Solution, under the guiding of present inventive concept, those skilled in the art can carry out various modifications and improvements, and appended claims are summarised
The scope of the present invention.
Claims (7)
1. a kind of fluorene kind derivative containing aryl amine, it is characterised in that with the structure as shown in formula (1)：
Wherein：
The R1And R2Separately selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl,
One of ethylbenzene, xenyl, naphthyl, naphthylphenyl, triarylamine；
The Ar1And Ar2Phenyl is separately selected from, the alkyl-substituted phenyl of C1-10, xenyl, C1-10 is alkyl-substituted
One of xenyl, naphthyl, the alkyl-substituted naphthyls of C1-10, naphthylphenyl, triarylamine；
The bridge linkage group L1And L2It is independently selected from one of singly-bound, phenylene, biphenylene, naphthylene, sub- pyridine radicals；
On condition that R1And R2It is asynchronously H；
Ar skeleton structure is selected from following structures：
2. the fluorene kind derivative according to claim 1 containing aryl amine, it is characterised in that work as R1Or R2It is described when being not H
R1Or R2Selected from following structures：
3. the fluorene kind derivative according to claim 1 containing aryl amine, it is characterised in that the fluorenes class containing aryl amine
Derivative is selected from following structural formula：
4. application of the fluorene kind derivative containing aryl amine described in claim any one of 1-3 in organic electroluminescence device.
5. application according to claim 4, it is characterised in that the fluorene kind derivative containing aryl amine is used as organic electroluminescent
The phosphorescent light body material of device.
6. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer, organic light emission on the substrate
Functional layer and cathode layer；Described organic luminescence function layer includes hole transmission layer, organic luminous layer and electron transfer layer, its
It is characterised by：
The material of main part of the organic luminous layer is to be one or more as any one of claim 1-3 containing aryl amine
Fluorene kind derivative.
7. a kind of organic electroluminescence device according to claim 6, it is characterised in that the luminescent layer is by material of main part
With luminescent dye composition, the luminescent dye is phosphorescent coloring.
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| CN107383003B (en) * | 2017-06-15 | 2019-11-29 | 浙江工业大学 | A kind of synthesis and application of the tri-arylamine group dye sensitizing agent containing quinacridone |
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