CN110437208A - A kind of bis- carbazole benzene class phosphorescent light body material of 1,3-, its synthetic method and its application - Google Patents
A kind of bis- carbazole benzene class phosphorescent light body material of 1,3-, its synthetic method and its application Download PDFInfo
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Abstract
The invention discloses 1,3- of one kind, bis- carbazole benzene class phosphorescent light body material, its synthetic method and its applications, belong to photoelectric material applicating technology field.The present invention is obtained by simple synthetic route with N,-two carbazyl -1 of N ', 3- benzene is the blue phosphorescent material of main part of fixed structure unit, glass transition temperature is relatively high, it is with preferable hole and electron transport ability, good film-forming property and property stabilization, device efficiency is greater than 40Cd/A and poor efficiency is roll-offed under high illumination, is the ideal efficiently bipolar material of main part of blue phosphorescent.The glass transition temperature that the present invention solves common blue emitting phosphor material of main part is lower, and material stability itself is not high, and the problem of roll-off with high efficiency under high illumination, it is hindered to be widely used.
Description
Technical field
The invention belongs to photoelectric material applicating technology fields, and in particular to 1,3- of one kind, bis- carbazole benzene class phosphorescence host material
Material, its synthetic method and its application.
Technical background
Organic anthracene crystal has been found under high driving voltage since luminescence phenomenon from first time in 1963, and organic electroluminescent is existing
As obtaining the highest attention of scientists.1987, Deng Qingyun research group was put forward for the first time noncrystal thin using organic multilayer
The OLED structure of film reduces driving voltage, improves luminous intensity；Nineteen ninety Burroughes et al. reports macromolecule hair for the first time
Optical diode, organic electroluminescent research enters a completely new stage since then.
Mostly use Subjective and Objective structure in present electrophosphorescence device greatly, i.e., by phosphorescent emissions substance with certain dense
Degree is entrained in main substance, to avoid T-T annihilation, improves phosphorescent emissions efficiency.Nearly ten years, organic light emission
Diode is because having many advantages, such as that response is fast, brightness is high, operating voltage is low, can be widely used in Multifunctional flat due to flexibility display
In the display of face.
Forrest and Thompson in 1999 etc. is by green light phosphor material Ir (ppy)3With the doped in concentrations profiled of 6wt% 4,
In 4 '-N, N '-two carbazole-biphenyl (CBP) material of main part, and introduce hole resistance shelves material 2,9- dimethyl -4,7- diphenyl -
1,10- Phen (BCP).It obtaining green light OLED maximum external quantum efficiency (EQE) and reaches 8%, power efficiency reaches 31lm/W,
Electrochromic fluorescent devices are substantially exceeded, cause highest attention of the people to heavy metal complex luminescent material immediately.
Forrest in 2000 etc. is by Ir (ppy)3It is entrained in electron-transporting type main body 3- phenyl -4- (1 '-naphthalene) -5- benzene
Base -1,2, in 4- triazole (TAZ), obtaining maximum power efficiency is 40lm/W, so as to cause more more people's investments to a huge sum of money
Belong to the research of Ir complex.
Forrest and Thompson in 2003 etc. is by day blue light main body FIrpic with the doped in concentrations profiled of (7,5 ± 0,8) wt%
In N, the material of main part of-two carbazole -3,5- benzene (mCP) of N ', obtaining maximum and send out big luminous power efficiency is 8,9 ± 0,9lm/W,
To open the epoch that heavy metal coordination compound is applied in blue-light device.
In recent years, there are many reports about efficient Blue-light emitting host material.Cheng etc. (Adv, Mater, 2010,
22,2468) FIrpic is entrained in phosphorus oxygen main body 4-N- carbazole phenyl diphenyl phosphorus oxygen (BCPO) with the concentration of 8wt%, device
The maximum current efficiency of part reaches 45Cd/A, and maximum external quantum efficiency EQE has reached 23,5%, this efficiency should for recently with
The peak efficiency of FIrpic doping, but it causes efficiency roll-off too fast since carrier is uneven under high illumination.
Since carbazole has high hole transport performance and high triplet energy, nowadays develop a series of containing carbazole unit
Phosphorescent light body material.Most-often used blue emitting phosphor material of main part is N,-two carbazyl -1,3- benzene (m-CP) of N ', this material three
Weight state energy is 2,9eV, and Efficient devices external quantum efficiency is promoted to 15%.But the glass transition temperature of m-CP is lower, and material
Expect that stability itself is not high, and roll-off under high illumination with high efficiency, it is hindered to be widely used, which solves.
Summary of the invention
The present invention solves the technical problem of the glass transition temperature of common blue emitting phosphor material of main part is lower, material sheet
Body stability is not high, and the problem of roll-off with high efficiency under high illumination, it is hindered to be widely used, and provides one kind 1,3- bis-
Carbazole benzene class phosphorescent light body material, its synthetic method and its application.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
This blue phosphorescent material of main part provided by the invention has the structure as shown in following formula I:
Wherein, R1、R2、R3、R4、R5There are several to be chosen to be hydrogen-based in five groups；R1And R2And R3And R4And R5It selects respectively
From hydrogen-based, carbazyl, tert-butyl -9- carbazyl, diphenylamines, diphenylphosphine oxygroup, azepine -9- carbazyl, diaza -9- carbazole
Base, triphenyl silicon substrate, to phenyl benzimidazole groups, phenyl benzimidazole groups, to triphenylamine base, dimethyl to triphenylamine base,
Two generation tert-butyl carbazole bases, 1- naphthalene replace to triphenylamine base, 2- naphthalene replace to triphenylamine base, 3,6- di-t-butyl carbazole phenyl,
Two generations 3,6- di-t-butyl carbazole phenyl, dibenzothiophenes, dibenzofurans, dibenzothiophene dioxide, an oxidation dibenzo
Thiophene, 2- pyridine, 3- pyridine, 4- pyridine, phenanthro- imidazoles, N- replace one of phenanthro- imidazoles；The R1、R2、R3、R4、R5Five
In a group using hydrogen-based be group include 3 or 4.
In the above-mentioned technical solutions, the R1、R2、R3、R4、R5Five groups it is selected specifically include it is as follows:
R1For carbazyl, R2,R3,R4,R5For hydrogen-based；Or R2For carbazyl, R3,R4,R5,R1For hydrogen-based；Or R3For carbazyl,
R2,R1,R4,R5For hydrogen-based；Or R1For diphenylphosphine oxygroup, R2,R3,R4,R5For hydrogen-based；Or R2For diphenylphosphine oxygroup, R3,R4,
R5,R1For hydrogen-based；Or R3For diphenylphosphine oxygroup, R2,R1,R4,R5For hydrogen-based；Or R1,R2For diphenylphosphine oxygroup, R3,R4,R5For
Hydrogen-based；Or R1,R3For diphenylphosphine oxygroup, R2,R4,R5For hydrogen-based；Or R1,R4For diphenylphosphine oxygroup, R3,R2,R5For hydrogen-based；
Or R1,R5For diphenylphosphine oxygroup, R3,R4,R2For hydrogen-based；Or R3,R2For diphenylphosphine oxygroup, R1,R4,R5For hydrogen-based；Or R4,R2
For diphenylphosphine oxygroup, R1,R3,R5For hydrogen-based；Or R5,R2For diphenylphosphine oxygroup, R1,R4,R3For hydrogen-based；Or R1For pyridyl group,
R2,R3,R4,R5For hydrogen-based；Or R2For pyridyl group, R3,R4,R5,R1For hydrogen-based；Or R3For pyridyl group, R2,R1,R4,R5For hydrogen-based；Or
R1,R2For pyridyl group, R3,R4,R5For hydrogen-based；Or R1,R3For pyridyl group, R2,R4,R5For hydrogen-based；Or R1,R4For pyridyl group, R3,R2,
R5For hydrogen-based；Or R1,R5For pyridyl group, R3,R4,R2For hydrogen-based；Or R3,R2For pyridyl group, R1,R4,R5For hydrogen-based；Or R4,R2For
Pyridyl group, R1,R3,R5For hydrogen-based；Or R5,R2For pyridyl group, R1,R4,R3For hydrogen-based；Or R1For two generation tert-butyl substituted carbazole bases,
R2,R3,R4,R5For hydrogen-based；Or R2For two generation tert-butyl substituted carbazole bases, R3,R4,R5,R1For hydrogen-based；Or R3For two generation tert-butyls
Substituted carbazole base, R2,R1,R4,R5For hydrogen-based；Or R1For hexichol amido, R2,R3,R4,R5For hydrogen-based；Or R2For hexichol amido, R3,
R4,R5,R1For hydrogen-based；Or R3For hexichol amido, R2,R1,R4,R5For hydrogen-based；Or R1For triphenylamine base, R2,R3,R4,R5For hydrogen-based；
Or R2For triphenylamine base, R3,R4,R5,R1For hydrogen-based；Or R3For triphenylamine base, R2,R1,R4,R5For hydrogen-based；Or R1For azepine -9- click
Oxazolyl, R2,R3,R4,R5For hydrogen-based；Or R2For azepine -9- carbazyl, R3,R4,R5,R1For hydrogen-based；Or R3For azepine -9- carbazole
Base, R2,R1,R4,R5For hydrogen-based；Or R1For dibenzothiophene, R2,R3,R4,R5For hydrogen-based；Or R2For dibenzothiophene, R3,
R4,R5,R1For hydrogen-based；Or R3For dibenzothiophene, R2,R1,R4,R5For hydrogen-based.
In the above-mentioned technical solutions, the R1、R2、R3、R4、R5The compound of the selected determination of five groups, including it is described
Three substituents, four substituents, five substituents of compound, all can be used as the material of main part.
In the above-mentioned technical solutions, a kind of synthetic method of 1,3-, bis- carbazole benzene class phosphorescent light body material as described above,
The synthetic method includes the following steps:
(1) m-dibromobenzene and carbazole are dissolved in 1,3- Dimethyl Propylene Urea (DMPU), are heated to 1800 DEG C and react back
48h is flowed, 1,3-, bis- carbazole benzene (mCP) is obtained；
(2) N, N '-dimethyl benzamide (NBS) and mCP are dissolved in n,N-Dimethylformamide (DMF), room temperature is anti-
It answers, obtains bromo- 1,3-, the bis- carbazyl benzene of 3-；
(3) bromo- 1,3-, the bis- carbazyl benzene of 3- and conjunction diborate are dissolved in tetrahydrofuran (THF) back flow reaction, obtain 3-
Two carbazyl benzene of borate -1,3-；
(4) two carbazyl benzene of 3- borate -1,3- is taken to obtain the 3- phenyl-that o-, m-, contraposition bromine replaces using suzuki reaction
Bis- carbazyl benzene of 1,3-；
(5) it reacts to form the main body that last o-, m-, contraposition replaces using ullmann reaction or suzuki reaction or hexichol phosphorus oxygen
Luminescent material.
In the above-mentioned technical solutions, the R in the Formulas I1For diphenylphosphine oxygroup, R2、R3、R4And R5To be named as when hydrogen-based
Bis- carbazyl benzene (mCPoPO) of 3- (2- diphenyl phosphorus oxygen) phenyl -1,3-, the mCPoPO synthetic method include the following steps:
Step a: the m-dibromobenzene of 1~3mol and 2.5~7.5mol carbazole are dissolved in DMPU (the 1,3- diformazan of 250mL
Base trimethylene urea) in, 180 DEG C of reaction reflux 48h are heated to, the mCP (1,3- bis- carbazole benzene) of 0.94~2.82mol is obtained；
Step b: the mCP of NBS (N, N '-dimethyl benzamide) and 0.92~2.76mol of 0.9~2.7mol is dissolved in
In DMF, room temperature reaction obtains bromo- 1,3-, the bis- carbazyl benzene of 3- of 0.89~2.67mol；
Step c: based on molfraction, by the conjunction of the 3- of 0.85~2.55mol bromo- 1,3- bis- carbazyl benzene and 1~3mol
Diborate is dissolved in the tetrahydrofuran reflux of 1L, obtains the bis- carbazyl benzene of 3- borate -1,3- of 0.75~2.25mol；
Step d: two carbazole of 3- (2- bromobenzene) base -1,3- for 0.7~2.1mol that adjacent bromine replaces is obtained using suzuki reaction
Base benzene；
Step e: in liquid nitrogen environment, the tetrahydrofuran of 500mL and 3- (2- bromobenzene) base -1,3- of 0.5~1.5mol are taken
The mixing of two carbazyl benzene, the n-BuLi for instilling 0.5~1.5mol react 3h, add 0.6~diphenylphosphine liter l.8mol
To room temperature reaction 4h, the hydrogen peroxide Oxidation at room temperature of 1~3mol is added, column chromatographs to get 3- (2- diphenyl phosphorus oxygen) phenyl -1,
Bis- carbazyl benzene (mCPoPO) of 3-.
In the above-mentioned technical solutions, the R in the Formulas I2For diphenylphosphine oxygroup, R1、R3、R4And R5When for hydrogen-based, name
For bis- carbazyl benzene (mCPmPO) of 3- (3- diphenyl phosphorus oxygen) phenyl -1,3-, the synthetic method of the mCPmPO includes following step
It is rapid:
Step a: the carbazole of 1~3mol m-dibromobenzene and 2.5~7.5mol is dissolved in the DMPU of 250mL, is heated to
180 DEG C of reactions reflux 48h, obtain the mCP (1,3- bis- carbazole benzene) of 0.94~2.82mol using ullmann reaction；
Step b: the mCP of NBS (N, N '-dimethyl benzamide) and 0.92~2.76mol of 0.9~2.7mol is dissolved in
In the DMF of 500mL, room temperature reaction obtains bromo- 1,3-, the bis- carbazyl benzene of 3- of 0.89~2.67mol；
Step c: the bromo- bis- carbazyl benzene of 1,3- of the 3- of 0.85~2.6mol and the conjunction diborate of 1~3mol are dissolved in
The reflux of 1L tetrahydrofuran, obtains the bis- carbazyl benzene of 3- borate -1,3- of 0.75~2.25mol；
Step d: two carbazole of 3- (3- bromobenzene) base -1,3- for 0.7~2.1mol that adjacent bromine replaces is obtained using suzuki reaction
Base benzene；
Step e: in liquid nitrogen environment, the tetrahydrofuran of 500mL and 3- (3- bromobenzene) base -1,3- of 0.5~1.5mol are taken
The mixing of two carbazyl benzene is slowly dropped into the n-BuLi reaction of 0.5~1.5mol, the diphenylphosphine liter of 0.6~1.8mol is added
To room temperature reaction, the hydrogen peroxide Oxidation at room temperature of 1~3mol is added, column chromatographs to get mCPmPO.
In the above-mentioned technical solutions, the R in the Formulas I2For benzimidazolyl, R1、R3、R4And R5When for hydrogen-based, it is named as
Bis- carbazyl benzene (mCPmBI) of 3- (3- benzimidazolyl) phenyl -1,3-, the synthetic method of the mCPmBI, including walk as follows
It is rapid:
Step a: 1~3mol m-dibromobenzene and 2.5~7.5mol carbazole are dissolved in DMPU (the 1,3- dimethyl of 250mL
Trimethylene urea) in, 180 DEG C of reaction reflux 48h are heated to, mCP (1,3- bis- click of 0.95~2.85mol is obtained using ullmann reaction
Azoles benzene)；
Step b: the mCP of the NBS (N, N '-dimethyl benzamide) of 0.9~2.7mol and 0.9~2.7mol are dissolved in 1L
DMF in, room temperature reaction, obtain bromo- 1,3-, the bis- carbazyl benzene of 3- of 0.85~2.55mol；
Step c: the bromo- bis- carbazyl benzene of 1,3- of the 3- of 0.85~2.6mol and the conjunction diborate of 1~3mol are dissolved in
THF (tetrahydrofuran) reflux, obtains bis- carbazyl benzene of 3- borate -1,3-；
Step d: two carbazyl benzene of 3- borate -1,3- and bromo benzimidazole are formed into chemical combination using ullmann reaction
Object, column chromatograph to get mCPmBI.
In the above-mentioned technical solutions, the R in the Formulas I2、R4For 3- pyridyl group, R1,R3,R5When for hydrogen-based, it is named as 3-
(3,5- bis- (3- pyridyl group) phenyl -1,3-, bis- carbazyl benzene (mCPDPP), the synthetic method of the mCPDPP, including walk as follows
It is rapid:
Step a: the 250mL that the m-dibromobenzene of 1~3mol and 2.5~7.5mol carbazole are dissolved in DMPU (1,3- bis-
Methyl trimethylene urea) in, be heated to 180 DEG C of reactions reflux 48h, using ullmann reaction obtain 0.95~2.85mol mCP (1,
Bis- carbazole benzene of 3-)；
Step b: the mCP of the NBS (N, N '-dimethyl benzamide) of 0.9~2.7mol and 0.9~2.7mol are dissolved in 1L
DMF in, room temperature reaction, obtain bromo- 1,3-, the bis- carbazyl benzene of 3- of 0.85~2.55mol；
Step c: the bromo- bis- carbazyl benzene of 1,3- of the 3- of 0.8~2.4mol and the conjunction diborate of 1~3mol are dissolved in
THF (tetrahydrofuran) reflux, forms 0.75~2.25mol3- borate -1,3-, bis- carbazyl benzene；
Step d: using suzuki reaction by the two carbazyl benzene of 3- borate -1,3- of 0.7~2.1mol and 0.75~
(3- the pyridyl group)-bromobenzene of 3,5- bis- of 2.25mol forms compound, and column chromatographs to get mCPDPP.
In the above-mentioned technical solutions, a kind of application of 1,3-, bis- carbazole benzene class phosphorescent light body material as described above: the material
Material is applied to the blue phosphorescent material of main part of Organic Light Emitting Diode (OLED).
The beneficial effects of the present invention are:
(1) present invention is obtained by simple synthetic route with N, and-two carbazyl -1,3- benzene of N ' is fixed structure unit
Blue phosphorescent material of main part, glass transition temperature is relatively high, and triplet energies are generally greater than 2,7eV, and have preferable hole
And electron transport ability, good film-forming property and property stabilization, device efficiency is greater than 40Cd/A and poor efficiency is roll-offed under high illumination, is
The ideal efficiently bipolar material of main part of blue phosphorescent；
(2) compound provided by the invention with structure shown in Formulas I is a kind of high triplet energy and has good empty
The efficient blue phosphorescent material of main part in cave and electron transport ability has good thermal stability, blue phosphorus provided by the invention
The bipolar material of main part of light and phosphorescent light body material N commonly used in the prior art,-two carbazyl -1,3- benzene (mCP) of N ' are compared, this
In the case where triplet energies keep higher state, the transmittability of hole and electronics is significantly improved the invention compound,
It applies in organic electroluminescence device, which is not only significantly improved on light emission luminance and efficiency, and highlighted
Degree condition (1000cd/m2) under, efficiency roll-off is smaller, is ideal blue phosphorescent material of main part.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing, in which:
The schematic arrangement of Fig. 1, material of main part of the present invention；
Fig. 2, material prepares the structural schematic diagram of organic electroluminescence device based on the compounds of this invention；
The room temperature Ultraluminescence spectrogram of Fig. 3, the compounds of this invention mCPmPO；
The ciency-luminance performance diagram of device 2 in Fig. 4, embodiment 6.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's all other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
This blue phosphorescent material of main part provided by the invention has the structure as shown in following formula I:
Wherein, R1、R2、R3、R4、R5There are several to be chosen to be hydrogen-based in five groups；R1And R2And R3And R4And R5It selects respectively
From hydrogen-based, carbazyl, tert-butyl -9- carbazyl, diphenylamines, diphenylphosphine oxygroup, azepine -9- carbazyl, diaza -9- carbazole
Base, triphenyl silicon substrate, to phenyl benzimidazole groups, phenyl benzimidazole groups, to triphenylamine base, dimethyl to triphenylamine base,
Two generation tert-butyl carbazole bases, 1- naphthalene replace to triphenylamine base, 2- naphthalene replace to triphenylamine base, 3,6- di-t-butyl carbazole phenyl,
Two generations 3,6- di-t-butyl carbazole phenyl, dibenzothiophenes, dibenzofurans, dibenzothiophene dioxide, an oxidation dibenzo
Thiophene, 2- pyridine, 3- pyridine, 4- pyridine, phenanthro- imidazoles, N- replace one of phenanthro- imidazoles.
Above-mentioned R1、R2、R3、R4、R5The specific structure and title of each substituent group are shown in Table 1
The synthetic method for 1,3-, the bis- carbazole benzene class phosphorescent light body material that the present invention announces, comprising the following steps:
Step 1: m-dibromobenzene and carbazole are dissolved in DMPU (1,3- Dimethyl Propylene Urea), are heated to 180 DEG C of reactions
Flow back 48h, obtains mCP (1,3- bis- carbazole benzene) using ullmann reaction；
Step 2: NBS (N, N '-dimethyl benzamide) and mCP are dissolved in DMF, 6h is reacted at room temperature, obtains
To the bromo- bis- carbazyl benzene of 1,3- of 3-；
Step 3: bromo- 1,3-, the bis- carbazyl benzene of 3- and conjunction diborate are dissolved in THF (tetrahydrofuran) reflux for 24 hours, shape
At two carbazyl benzene of 3- borate -1,3-；
Step 4: the two carbazyl benzene of 3- phenyl -1,3- that o-, m-, contraposition bromine replaces is obtained using suzuki reaction；
Step 5: it reacts to form last o-, m-, contraposition and replace using ullmann reaction or suzuki reaction or hexichol phosphorus oxygen
Main body luminescent material.
The embodiment of the present invention 1 is provided as the R in Formulas I2、R4、R5And R3For hydrogen-based, R1Chemical combination when for diphenylphosphine oxygroup
The preparation method of object, the Compound nomenclature are bis- carbazyl benzene (referred to as mCPoPO) of 3- (2- diphenyl phosphorus oxygen) phenyl -1,3-.
The embodiment of the present invention 2 is provided as the R in Formulas I1、R3、R4And R5For hydrogen-based, R2Compound when diphenylphosphine oxygroup
Preparation method, the Compound nomenclature be bis- carbazyl benzene (referred to as mCPmPO) of 3- (3- diphenyl phosphorus oxygen) phenyl -1,3-.
The embodiment of the present invention 3 is provided as the R in Formulas I1、R2、R4And R5For hydrogen-based, R3Chemical combination when for diphenylphosphine oxygroup
The preparation method of object, the Compound nomenclature are bis- carbazyl benzene (referred to as mCPpPO) of 3- (4- diphenyl phosphorus oxygen) phenyl -1,3-.
The embodiment of the present invention 4 is provided as the R in Formulas I2And R4For 3- pyridyl group, R1、R3、R5For the preparation method of hydrogen-based,
The Compound nomenclature is two carbazyl benzene (referred to as mCPDPP) of 3- (3,5- bis- (3- pyridine) base) phenyl -1,3-.
The embodiment of the present invention 5 is provided as the R in Formulas I1、R3、R4And R5For hydrogen-based, R2Chemical combination when for benzimidazolyl
The preparation method of object, the Compound nomenclature are bis- carbazyl benzene (referred to as mCPmBI) of 3- (3- benzimidazolyl) phenyl -1,3-.
The embodiment of the present invention 6 is additionally provided as the R in Formulas I2、R3、R4And R5For hydrogen-based, R1Chemical combination when for benzimidazolyl
The preparation method of object, bis- carbazyl benzene (referred to as mCPoBI) of 3- (2- benzimidazolyl) phenyl -1,3-.
All compounds of the present invention can be used as Organic Light Emitting Diode (OLED) blue phosphorescent material of main part.
Embodiment 1: as the R in Formulas I1For diphenylphosphine oxygroup, R2、R3、R4And R5To be named as 3- (2- diphenyl when hydrogen-based
Phosphorus oxygen) two carbazyl benzene (2- (9- (3- (9H-carbazol-9-yl) phenyl) -9H-carbazol-3-yl) of phenyl -1,3-
Phenyl) diphen-ylp hosphine oxide (mCPoPO) its structural formula difference is as follows:
MCPoPO of the present invention can be synthesized by following method.
Step a: 1mol m-dibromobenzene and 2.5mol carbazole are dissolved in 250mL DMPU (1,3- Dimethyl Propylene Urea),
180 DEG C of reaction reflux 48h are heated to, obtain 0.94mol mCP (1,3- bis- carbazole benzene) using ullmann reaction；
Step b: 0.9mol NBS (N, N '-dimethyl benzamide) and 0.92mCP are dissolved in DMF, in room temperature condition
Lower reaction 6h obtains bromo- 1,3-, the bis- carbazyl benzene of 0.89mol 3-；
Step c: the bromo- bis- carbazyl benzene of 1,3- of 0.85mol 3- and 1.0mol are closed into diborate and are dissolved in 1LTHF (tetrahydro
Furans) it flows back for 24 hours, form bis- carbazyl benzene of 0.75mol 3- borate -1,3-；
Step d: the two carbazyl benzene of 0.7mol 3- (2- bromobenzene) base -1,3- that adjacent bromine replaces is obtained using suzuki reaction；
Step e: in liquid nitrogen environment, 500mL tetrahydrofuran and 0.5mol 3- (2- bromobenzene) base-are added in reaction flask
1,3- bis- carbazyl benzene is slowly dropped into 0.5mol n-BuLi reaction 3h, and 0.6mol diphenylphosphine is then added and is warmed to room temperature again
4h is reacted, 1mol hydrogen peroxide is eventually adding and aoxidizes 4h at room temperature, chromatograph to obtain compound 3- (2- diphenyl phosphorus oxygen) benzene by column
Two carbazyl benzene (mCPoPO) of base -1,3-.
Yield: 65%.APCI(m/z):calcd for C48H33N2OP, 684,2；Found, 685,5 (M+H)+。
Embodiment 2: as R in Formulas I2For diphenylphosphine oxygroup, R1、R3、R4And R5When for hydrogen-based, it is named as 3- (3- diphenyl
Phosphorus oxygen) two carbazyl benzene (3- (9- (3- (9H-carbazol-9-yl) phenyl) -9H-carbazol-3-yl) of phenyl -1,3-
Phenyl) diphenylph osphine oxide (mCPmPO), structural formula is as follows:
MCPmPO of the present invention can be synthesized by following method.
Step a: 1mol dibromobenzene and 2.5mol carbazole are dissolved in 250mL DMPU (1,3- Dimethyl Propylene Urea) by between,
180 DEG C of reaction reflux 48h are heated to, obtain 0.94mol mCP (1,3- bis- carbazole benzene) using ullmann reaction；
Step b: 0.9mol NBS (N, N '-dimethyl benzamide) and 0.92mCP are dissolved in DMF, in room temperature condition
Lower reaction 6h obtains bromo- 1,3-, the bis- carbazyl benzene of 0.89mol 3-；
Step c: the bromo- bis- carbazyl benzene of 1,3- of 0.85mol 3- and 1.0mol are closed into diborate and are dissolved in 1LTHF (tetrahydro
Furans) it flows back for 24 hours, form bis- carbazyl benzene of 0.75mol 3- borate -1,3-；
Step d: the two carbazyl benzene of 0.7mol 3- (2- bromobenzene) base -1,3- that adjacent bromine replaces is obtained using suzuki reaction；
Step e: in liquid nitrogen environment, 500mL tetrahydrofuran and 0.5mol 3- (2- bromobenzene) base-are added in reaction flask
1,3- bis- carbazyl benzene is slowly dropped into 0.5mol n-BuLi reaction 3h, and 0.6mol diphenylphosphine is then added and is warmed to room temperature again
4h is reacted, 1mol hydrogen peroxide is eventually adding and aoxidizes 4h at room temperature, chromatograph to obtain compound 3- (3- diphenyl phosphorus oxygen) benzene by column
Two carbazyl benzene (mCPmPO) of base -1,3-.
Yield 68%.APCI(m/z):calcd for C48H33N2OP, 684,2；Found, 685,7 (M+H)+。
Embodiment 3: as R in Formulas I2For diphenylphosphine oxygroup, R1、R3、R4And R5When for hydrogen-based, it is named as 3- (4- diphenyl
Phosphorus oxygen) two carbazyl benzene (4- (9- (3- (9H-carbazol-9-yl) phenyl) -9H-carbazol-3-yl) of phenyl -1,3-
Phenyl) diphenylph osphine oxide (mCPpPO), structural formula is as follows: its structural formula is as follows:
MCPpPO of the present invention can be synthesized by following method.
Step a: 1mol m-dibromobenzene and 2.5mol carbazole are dissolved in 250mL DMPU (1,3- Dimethyl Propylene Urea),
180 DEG C of reaction reflux 48h are heated to, obtain 0.94mol mCP (1,3- bis- carbazole benzene) using ullmann reaction；
Step b: 0.9mol NBS (N, N '-dimethyl benzamide) and 0.92mCP are dissolved in DMF, in room temperature condition
Lower reaction 6h obtains bromo- 1,3-, the bis- carbazyl benzene of 0.89mol 3-；
Step c: the bromo- bis- carbazyl benzene of 1,3- of 0.85mol 3- and 1.0mol are closed into diborate and are dissolved in 1LTHF (tetrahydro
Furans) it flows back for 24 hours, form bis- carbazyl benzene of 0.75mol 3- borate -1,3-；
Step d: the two carbazyl benzene of 0.7mol 3- (2- bromobenzene) base -1,3- that adjacent bromine replaces is obtained using suzuki reaction；
Step e: in liquid nitrogen environment, 500mL tetrahydrofuran and 0.5mol 3- (2- bromobenzene) base-are added in reaction flask
1,3- bis- carbazyl benzene is slowly dropped into 0.5mol n-BuLi reaction 3h, and 0.6mol diphenylphosphine is then added and is warmed to room temperature again
4h is reacted, 1mol hydrogen peroxide is eventually adding and aoxidizes 4h at room temperature, chromatograph to obtain compound 3- (4- diphenyl phosphorus oxygen) benzene by column
Two carbazyl benzene (mCPpPO) of base -1,3-.
Yield: 75%.APCI(m/z):calcd for C48H33N2OP, 684,2；Found, 685,6 (M+H)+。
Embodiment 4: as R in Formulas I2For benzimidazolyl, R1、R3、R4And R5When for hydrogen-based, material designation is 3- (3- benzo
Imidazole radicals) bis- carbazyl benzene (mCPmBI) of phenyl -1,3-, structural formula is as follows:
Above-mentioned mCPmBI can be synthesized by following method:
Step a: 1mol m-dibromobenzene and 2.5mol carbazole are dissolved in 250mL DMPU (1,3- Dimethyl Propylene Urea),
180 DEG C of reaction reflux 48h are heated to, obtain 0.95mol mCP (1,3- bis- carbazole benzene) using ullmann reaction；
Step b: 0.90mol NBS (N, N '-dimethyl benzamide) and 0.90mol mCP are dissolved in 1LDMF, in room
6h is reacted under the conditions of temperature, obtains bromo- 1,3-, the bis- carbazyl benzene of 0.85mol 3-；
Step c: the bromo- bis- carbazyl benzene of 1,3- of 0.80mol 3- and 1mol are closed into the THF that diborate is dissolved in 500mL
(tetrahydrofuran) flows back for 24 hours, forms bis- carbazyl benzene of 0.75mol 3- borate -1,3-；
Step d: two carbazyl benzene of 3- borate -1,3- and a bromo benzimidazole are formed finally using ullmann reaction
Compound, chromatograph to obtain bis- carbazyl benzene (mCPmBI) of compound 3- (3- benzimidazole) phenyl -1,3- by column.Yield:
80%.APCI(m/z):calcd for C49H32N4, 676,3；Found, 677,4 (M+H)+。
Embodiment 5: as R in Formulas I2、R4For 3- pyridyl group, R1,R3,R5When for hydrogen-based, material designation is 3- (3,5- bis- (3-
Pyridyl group) two carbazyl benzene (mCPDPP) of phenyl -1,3-.Its structural formula is as follows:
Above-mentioned mCPDPP can be synthesized by following method:
Step a: 1mol m-dibromobenzene and 2.5mol carbazole are dissolved in 250mL DMPU (1,3- Dimethyl Propylene Urea),
180 DEG C of reaction reflux 48h are heated to, obtain 0.95mol mCP (1,3- bis- carbazole benzene) using ullmann reaction；
Step b: 0.90mol NBS (N, N '-dimethyl benzamide) and 0.90mol mCP are dissolved in 1LDMF, in room
6h is reacted under the conditions of temperature, obtains bromo- 1,3-, the bis- carbazyl benzene of 0.85mol 3-；
Step c: the bromo- bis- carbazyl benzene of 1,3- of 0.80mol 3- and 1mol are closed into the THF that diborate is dissolved in 500mL
(tetrahydrofuran) flows back for 24 hours, forms bis- carbazyl benzene of 0.75mol 3- borate -1,3-；
Step d: utilize suzuki reaction by two carbazyl benzene of 0.70mol 3- borate -1,3- and 0.75mol 3,5- bis-
(3- pyridyl group)-bromobenzene forms last compound, chromatographs to obtain compound 3- (3- benzimidazole) phenyl -1,3- bis- by column
Carbazyl benzene (mCPDPP).
Yield: 82%.APCI(m/z):calcd for C46H30N4, 638,2；Found, 639,4 (M+H)+。
Embodiment 6: device is prepared using mCPmPO as blue phosphorescent material of main part.
It is then dry in 105 DEG C of vacuum by ito glass in succession in cleaning agent and deionized water with ultrasonic cleaning 30min
Dry 2h, then ito glass is put into the CFx plasma treatment that 1min is carried out in plasma reactor, it is transmitted to preparation in vacuum chamber
Organic film and metal electrode are prepared into device for mCPmPO as material of main part by the method for vacuum evaporation.
This experiment apparatus structure are as follows:
ITO/MoO3(20nm)/NPB(40nm)/mCP(5nm)/mCPmPO-FIrpic(20nm)/Tm PyPB(40nm)/
LiF(1nm)/Al。
Embodiment 7: device is prepared using mCPDPP as blue phosphorescent material of main part.
It is then dry in 105 DEG C of vacuum by ito glass in succession in cleaning agent and deionized water with ultrasonic cleaning 30min
Dry 2h, then ito glass is put into the CFx plasma treatment that 1min is carried out in plasma reactor, it is transmitted to preparation in vacuum chamber
Organic film and metal electrode are prepared into device for mCPDPP as material of main part by the method for vacuum evaporation.
This experiment apparatus structure are as follows:
ITO/MoO3(20nm)/NPB(40nm)/mCP(5nm)/mCPDPP-FIrpic(20nm)/Tm PyPB(40nm)/
LiF(1nm)/Al。
Embodiment 8: device is prepared using mCPmBI as blue phosphorescent material of main part.
It is then dry in 105 DEG C of vacuum by ito glass in succession in cleaning agent and deionized water with ultrasonic cleaning 30min
Dry 2h, then ito glass is put into the CFx plasma treatment that 1min is carried out in plasma reactor, it is transmitted to preparation in vacuum chamber
Organic film and metal electrode are prepared into device for mCPmBI as material of main part by the method for vacuum evaporation.
This experiment apparatus structure are as follows:
ITO/MoO3(20nm)/NPB(40nm)/mCP(5nm)/mCPmBI-FIrpic(20nm)/Tm PyPB(40nm)/
LiF(1nm)/Al。
Embodiment 9: device is prepared using mCPoPO as blue phosphorescent material of main part.
Then ito glass is dried in vacuo in succession in cleaning agent and deionized water with ultrasonic cleaning 30min in 105 DEG C
2h, then ito glass is put into the CFx plasma treatment that 1min is carried out in plasma reactor, it is transmitted in vacuum chamber and is prepared with
Machine film and metal electrode are prepared into device for mCPoPO as material of main part by the method for vacuum evaporation.
This experiment apparatus structure are as follows:
ITO/MoO3(20nm)/NPB(40nm)/mCP(5nm)/mCPoPO-FIrpic(20nm)/TmP yPB(40nm)/
LiF(1nm)/Al。
Embodiment 10: device is prepared using mCPpPO as blue phosphorescent material of main part.
It is then dry in 105 DEG C of vacuum by ito glass in succession in cleaning agent and deionized water with ultrasonic cleaning 30min
Dry 2h, then ito glass is put into the CFx plasma treatment that 1min is carried out in plasma reactor, it is transmitted to preparation in vacuum chamber
Organic film and metal electrode are prepared into device for mCPpPO as material of main part by the method for vacuum evaporation.This experiment apparatus
Structure are as follows:
ITO/MoO3(20nm)/NPB(40nm)/mCP(5nm)/mCPpPO-FIrpic(20nm)/TmP yPB(40nm)/
LiF(1nm)/Al。
The device architecture of embodiment 6~10 is shown in Table 2, device 1~5.
R in table 1, formula 11、R2、R3、R4、R5The structure and title of each substituent group
Table 2, the device architecture that Organic Light Emitting Diode is prepared with the compounds of this invention
Made device 1 and document (Adv, Mater, 2010,22,5370；Adv, Funct, Mater, 2011,21,
1168) compared to test, made 1 efficiency of device is higher, and works as its light emission luminance from 10cd/m2Increase to 1000cd/m2When, efficiency
It roll-offs less than 2%, is detailed in Fig. 3.
The present invention can be widely applied to OLED large screen display higher to brightness requirement and OLED white-light illuminating, and institute
There is the glass transition temperature of compound at 120 DEG C or so, is far longer than 69 DEG C of mCP, is more suitable for industrialization.
All device results relatively obtain the efficiency highest of device 1, and efficiency roll-off is minimum under high illumination, and material
It is readily synthesized characterization, therefore is more suitable for industrialized production needs.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (10)
1. one kind 1, bis- carbazole benzene class phosphorescent light body material of 3-, which is characterized in that have the following structure formula (Formulas I):
Wherein, R1、R2、R3、R4、R5There are several to be chosen to be hydrogen-based in five groups；
R1And R2And R3And R4And R5Be respectively selected from hydrogen-based, carbazyl, tert-butyl -9- carbazyl, diphenylamines, diphenylphosphine oxygroup,
Azepine -9- carbazyl, diaza -9- carbazyl, triphenyl silicon substrate, to phenyl benzimidazole groups, phenyl benzimidazole groups, right
Triphenylamine base, dimethyl replace triphenylamine base, two generation tert-butyl carbazole bases, 1- naphthalene and replace triphenylamine base, 2- naphthalene to triphen
Amido, 3,6- di-t-butyl carbazole phenyl, two generations 3,6- di-t-butyl carbazole phenyl, dibenzothiophenes, dibenzofurans, dioxy
Change dibenzothiophenes, an oxidation dibenzothiophenes, 2- pyridine, 3- pyridine, 4- pyridine, phenanthro- imidazoles, N- to replace in phenanthro- imidazoles
One kind；
The R1、R2、R3、R4、R5In five groups using H base be group include 3 or 4.
2. 1,3-, bis- carbazole benzene class phosphorescent light body material according to claim 1, which is characterized in that the R1、R2、R3、R4、
R5Five groups it is selected specifically include it is as follows:
R1For carbazyl, R2,R3,R4,R5For hydrogen-based；Or R2For carbazyl, R3,R4,R5,R1For hydrogen-based；Or R3For carbazyl, R2,
R1,R4,R5For hydrogen-based；Or R1For diphenylphosphine oxygroup, R2,R3,R4,R5For hydrogen-based；Or R2For diphenylphosphine oxygroup, R3,R4,R5,
R1For hydrogen-based；Or R3For diphenylphosphine oxygroup, R2,R1,R4,R5For hydrogen-based；Or R1,R2For diphenylphosphine oxygroup, R3,R4,R5For hydrogen
Base；Or R1,R3For diphenylphosphine oxygroup, R2,R4,R5For hydrogen-based；Or R1,R4For diphenylphosphine oxygroup, R3,R2,R5For hydrogen-based；Or
R1,R5For diphenylphosphine oxygroup, R3,R4,R2For hydrogen-based；Or R3,R2For diphenylphosphine oxygroup, R1,R4,R5For hydrogen-based；Or R4,R2For
Diphenylphosphine oxygroup, R1,R3,R5For hydrogen-based；Or R5,R2For diphenylphosphine oxygroup, R1,R4,R3For hydrogen-based；Or R1For pyridyl group,
R2,R3,R4,R5For hydrogen-based；Or R2For pyridyl group, R3,R4,R5,R1For hydrogen-based；Or R3For pyridyl group, R2,R1,R4,R5For hydrogen-based；Or
R1,R2For pyridyl group, R3,R4,R5For hydrogen-based；Or R1,R3For pyridyl group, R2,R4,R5For hydrogen-based；Or R1,R4For pyridyl group, R3,R2,
R5For hydrogen-based；Or R1,R5For pyridyl group, R3,R4,R2For hydrogen-based；Or R3,R2For pyridyl group, R1,R4,R5For hydrogen-based；Or R4,R2For
Pyridyl group, R1,R3,R5For hydrogen-based；Or R5,R2For pyridyl group, R1,R4,R3For hydrogen-based；Or R1For two generation tert-butyl substituted carbazole bases,
R2,R3,R4,R5For hydrogen-based；Or R2For two generation tert-butyl substituted carbazole bases, R3,R4,R5,R1For hydrogen-based；Or R3For two generation tert-butyls
Substituted carbazole base, R2,R1,R4,R5For hydrogen-based；Or R1For hexichol amido, R2,R3,R4,R5For hydrogen-based；Or R2For hexichol amido, R3,
R4,R5,R1For hydrogen-based；Or R3For hexichol amido, R2,R1,R4,R5For hydrogen-based；Or R1For triphenylamine base, R2,R3,R4,R5For hydrogen-based；
Or R2For triphenylamine base, R3,R4,R5,R1For hydrogen-based；Or R3For triphenylamine base, R2,R1,R4,R5For hydrogen-based；Or R1For azepine -9- click
Oxazolyl, R2,R3,R4,R5For hydrogen-based；Or R2For azepine -9- carbazyl, R3,R4,R5,R1For hydrogen-based；Or R3For azepine -9- carbazole
Base, R2,R1,R4,R5For hydrogen-based；Or R1For dibenzothiophene, R2,R3,R4,R5For hydrogen-based；Or R2For dibenzothiophene, R3,
R4,R5,R1For hydrogen-based；Or R3For dibenzothiophene, R2,R1,R4,R5For hydrogen-based.
3. 1,3-, bis- carbazole benzene class phosphorescent light body material according to claim 2, which is characterized in that the R1、R2、R3、R4、
R5The compound of the selected determination of five groups, three substituents, four substituents, five substituents including the compound, all may be used
As the material of main part.
4. a kind of synthetic method of 1,3-, the bis- carbazole benzene class phosphorescent light body material as described in claims 1 to 3, feature exist
In the synthetic method includes the following steps:
(1) m-dibromobenzene and carbazole are dissolved in 1,3- Dimethyl Propylene Urea (DMPU), are heated to 1800 DEG C of reaction reflux, obtain
Bis- carbazole benzene (mCP) of 1,3-；
(2) N, N '-dimethyl benzamide (NBS) and mCP are dissolved in n,N-Dimethylformamide (DMF), react at room temperature, obtains
The bromo- bis- carbazyl benzene of 1,3- of 3-；
(3) bromo- 1,3-, the bis- carbazyl benzene of 3- and conjunction diborate are dissolved in tetrahydrofuran (THF) back flow reaction, obtain 3- boric acid
Two carbazyl benzene of ester -1,3-；
(4) two carbazyl benzene of 3- borate -1,3- is taken to obtain the 3- phenyl -1,3- that o-, m-, contraposition bromine replaces using suzuki reaction
Two carbazyl benzene；
(5) it is reacted using ullmann reaction or suzuki reaction or hexichol phosphorus oxygen and to form the main body that last o-, m-, contraposition replaces and shine
Material.
5. the synthetic method of 1,3-, bis- carbazole benzene class phosphorescent light body material according to claim 4, which is characterized in that described
R in Formulas I1For diphenylphosphine oxygroup, R2、R3、R4And R5To be named as two click of 3- (2- diphenyl phosphorus oxygen) phenyl -1,3- when hydrogen-based
Oxazolyl benzene (mCPoPO), the mCPoPO synthetic method, includes the following steps:
Step a: the m-dibromobenzene of 1~3mol and 2.5~7.5mol carbazole are dissolved in DMPU (the 1,3- dimethyl propylene of 250mL
Support urea) in, 180 DEG C of reaction reflux 48h are heated to, the mCP (1,3- bis- carbazole benzene) of 0.94~2.82mol is obtained；
Step b: the mCP of the NBS (N, N '-dimethyl benzamide) of 0.9~2.7mol and 0.92~2.76mol are dissolved in DMF
In, room temperature reaction obtains bromo- 1,3-, the bis- carbazyl benzene of 3- of 0.89~2.67mol；
Step c: based on molfraction, by two boron of conjunction of the 3- of 0.85~2.55mol bromo- 1,3-, bis- carbazyl benzene and 1~3mol
Acid esters is dissolved in the tetrahydrofuran reflux of 1L, obtains the bis- carbazyl benzene of 3- borate -1,3- of 0.75~2.25mol；
Step d: the two carbazyl benzene of 3- (2- bromobenzene) base -1,3- for 0.7~2.1mol that adjacent bromine replaces is obtained using suzuki reaction；
Step e: in liquid nitrogen environment, the tetrahydrofuran of 500mL and bis- click of 3- (2- bromobenzene) base -1,3- of 0.5~1.5mol are taken
The mixing of oxazolyl benzene, the n-BuLi for instilling 0.5~1.5mol react 3h, add 0.6~diphenylphosphine l.8mol rises to room
Temperature reaction 4h, adds the hydrogen peroxide Oxidation at room temperature of 1~3mol, and column chromatographs to get 3- (2- diphenyl phosphorus oxygen) phenyl -1,3- bis-
Carbazyl benzene (mCPoPO).
6. the synthetic method of 1,3-, bis- carbazole benzene class phosphorescent light body material according to claim 4, which is characterized in that described
R in Formulas I2For diphenylphosphine oxygroup, R1、R3、R4And R5When for hydrogen-based, it is named as 3- (3- diphenyl phosphorus oxygen) phenyl -1,3- bis-
Carbazyl benzene (mCPmPO), the synthetic method of the mCPmPO include the following steps:
Step a: the carbazole of 1~3mol m-dibromobenzene and 2.5~7.5mol is dissolved in the DMPU of 250mL, is heated to 180 DEG C
Reaction reflux, obtains the mCP (1,3- bis- carbazole benzene) of 0.94~2.82mol using ullmann reaction；
Step b: the mCP of NBS (N, N '-dimethyl benzamide) and 0.92~2.76mol of 0.9~2.7mol is dissolved in
In the DMF of 500mL, room temperature reaction obtains bromo- 1,3-, the bis- carbazyl benzene of 3- of 0.89~2.67mol；
Step c: the conjunction diborate of the bromo- bis- carbazyl benzene of 1,3- of the 3- of 0.85~2.6mol and 1~3mol is dissolved in 1L tetra-
The reflux of hydrogen furans, obtains the bis- carbazyl benzene of 3- borate -1,3- of 0.75~2.25mol；
Step d: the two carbazyl benzene of 3- (3- bromobenzene) base -1,3- for 0.7~2.1mol that adjacent bromine replaces is obtained using suzuki reaction；
Step e: in liquid nitrogen environment, the tetrahydrofuran of 500mL and bis- click of 3- (3- bromobenzene) base -1,3- of 0.5~1.5mol are taken
The mixing of oxazolyl benzene, instills the n-BuLi reaction of 0.5~1.5mol, and the diphenylphosphine that 0.6~1.8mol is added is warmed to room temperature instead
It answers, the hydrogen peroxide Oxidation at room temperature of 1~3mol is added, column chromatographs to get mCPmPO.
7. the synthetic method of 1,3-, bis- carbazole benzene class phosphorescent light body material according to claim 4, which is characterized in that described
R in Formulas I2For diphenylphosphine oxygroup, R1、R3、R4And R5When for hydrogen-based, it is named as 3- (4- diphenyl phosphorus oxygen) phenyl -1,3- bis-
Carbazyl benzene (mCPpPO), the synthetic method of the mCPpPO include the following steps:
Step a: the carbazole of the m-dibromobenzene of 1~3mol and 2.5~7.5mol is dissolved in DMPU (the 1,3- dimethyl of 250mL
Trimethylene urea) in, 180 DEG C of reaction reflux are heated to, obtain mCP (1,3- bis- carbazole of 0.94~2.82mol using ullmann reaction
Benzene)；
Step b: the mCP of the NBS (N, N '-dimethyl benzamide) of 0.9~2.7mol and 0.92~2.67mol are dissolved in 1L's
It in DMF, is reacting at room temperature, is obtaining bromo- 1,3-, the bis- carbazyl benzene of 3- of 0.89~2.67mol；
Step c: the conjunction diborate of the bromo- bis- carbazyl benzene of 1,3- of the 3- of 0.85~2.6mol and 1~3mol is dissolved in 1L's
THF (tetrahydrofuran) reflux, obtains the bis- carbazyl benzene of 3- borate -1,3- of 0.75~2.25mol；
Step d: the two carbazyl benzene of 3- (4- bromobenzene) base -1,3- for 0.7~2.1mol that adjacent bromine replaces is obtained using suzuki reaction；
Step e: in liquid nitrogen environment, 500mL tetrahydrofuran and bis- carbazole of 3- (4- bromobenzene) base -1,3- of 0.5~1.5mol are taken
The mixing of base benzene, the n-BuLi for instilling 0.5~1.5mol react 3h, and the diphenylphosphine for adding 0.6~1.8mol is warmed to room temperature
Reaction, the hydrogen peroxide that 1~3mol is added aoxidize at room temperature, and column chromatographs to get mCPpPO.
8. the synthetic method of 1,3-, bis- carbazole benzene class phosphorescent light body material according to claim 4, which is characterized in that described
R in Formulas I2For benzimidazolyl, R1、R3、R4And R5When for hydrogen-based, it is named as bis- click of 3- (3- benzimidazolyl) phenyl -1,3-
Oxazolyl benzene (mCPmBI), the synthetic method of the mCPmBI include the following steps:
Step a: 1~3mol m-dibromobenzene and 2.5~7.5mol carbazole are dissolved in DMPU (the 1,3- dimethyl trimethylene of 250mL
Urea) in, 180 DEG C of reaction reflux are heated to, the mCP (1,3- bis- carbazole benzene) of 0.95~2.85mol is obtained using ullmann reaction；
Step b: the mCP of the NBS (N, N '-dimethyl benzamide) of 0.9~2.7mol and 0.9~2.7mol are dissolved in 1L's
In DMF, room temperature reaction obtains bromo- 1,3-, the bis- carbazyl benzene of 3- of 0.85~2.55mol；
Step c: the conjunction diborate of the bromo- bis- carbazyl benzene of 1,3- of the 3- of 0.85~2.6mol and 1~3mol is dissolved in THF
(tetrahydrofuran) reflux, obtains bis- carbazyl benzene of 3- borate -1,3-；
Step d: forming compound for bis- carbazyl benzene of 3- borate -1,3- and bromo benzimidazole using ullmann reaction,
Column chromatographs to get mCPmBI.
9. the synthetic method of 1,3-, bis- carbazole benzene class phosphorescent light body material according to claim 4, which is characterized in that described
R in Formulas I2、R4For 3- pyridyl group, R1,R3,R5When for hydrogen-based, it is named as 3- (3,5- bis- (3- pyridyl group) phenyl -1,3-, bis- click
Oxazolyl benzene (mCPDPP), the synthetic method of the mCPDPP include the following steps:
Step a: the 250mL that the m-dibromobenzene of 1~3mol and 2.5~7.5mol carbazole are dissolved in DMPU (1,3- dimethyl
Trimethylene urea) in, 180 DEG C of reaction reflux are heated to, obtain mCP (1,3- bis- carbazole of 0.95~2.85mol using ullmann reaction
Benzene)；
Step b: the mCP of the NBS (N, N '-dimethyl benzamide) of 0.9~2.7mol and 0.9~2.7mol are dissolved in 1L's
In DMF, room temperature reaction obtains bromo- 1,3-, the bis- carbazyl benzene of 3- of 0.85~2.55mol；
Step c: the conjunction diborate of the bromo- bis- carbazyl benzene of 1,3- of the 3- of 0.8~2.4mol and 1~3mol is dissolved in THF (four
Hydrogen furans) reflux, form 0.75~2.25mol3- borate -1,3-, bis- carbazyl benzene；
Step d: using suzuki reaction by the two carbazyl benzene of 3- borate -1,3- of 0.7~2.1mol and 0.75~2.25mol
3,5- bis- (3- pyridyl group)-bromobenzenes form compound, and column chromatographs to get mCPDPP.
10. a kind of application of 1,3-, the bis- carbazole benzene class phosphorescent light body material as described in claims 1 to 3 any one, special
Sign is that the material is applied to the blue phosphorescent material of main part of Organic Light Emitting Diode (OLED).
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010044342A1 (en) * | 2008-10-15 | 2010-04-22 | コニカミノルタホールディングス株式会社 | Organic el element, organic el element manufacturing method, white organic el element, display device, and illumination device |
| WO2012078005A2 (en) * | 2010-12-10 | 2012-06-14 | 고려대학교 산학협력단 | Compounds having hole conducting property, co-adsorbent body comprising same, and dye-sensitized solar cell comprising the co-adsorbent body |
| CN102617446A (en) * | 2012-03-05 | 2012-08-01 | 西安近代化学研究所 | Synthesis method of 3, 5-N, N'-dicarbazoly benzene |
| US20130082591A1 (en) * | 2011-08-30 | 2013-04-04 | Semiconductor Energy Laboratory Co., Ltd. | Heterocyclic compound, light-emitting element, light-emitting device, electronic device, and lighting device |
| CN103430344A (en) * | 2011-03-14 | 2013-12-04 | 东丽株式会社 | Light-emitting element material and light-emitting element |
| CN103539819A (en) * | 2013-06-25 | 2014-01-29 | Tcl集团股份有限公司 | Bis-carbazolyl benzene compound, preparation method and application thereof and electroluminescent device |
-
2019
- 2019-08-27 CN CN201910793624.6A patent/CN110437208A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010044342A1 (en) * | 2008-10-15 | 2010-04-22 | コニカミノルタホールディングス株式会社 | Organic el element, organic el element manufacturing method, white organic el element, display device, and illumination device |
| WO2012078005A2 (en) * | 2010-12-10 | 2012-06-14 | 고려대학교 산학협력단 | Compounds having hole conducting property, co-adsorbent body comprising same, and dye-sensitized solar cell comprising the co-adsorbent body |
| CN103430344A (en) * | 2011-03-14 | 2013-12-04 | 东丽株式会社 | Light-emitting element material and light-emitting element |
| US20130082591A1 (en) * | 2011-08-30 | 2013-04-04 | Semiconductor Energy Laboratory Co., Ltd. | Heterocyclic compound, light-emitting element, light-emitting device, electronic device, and lighting device |
| CN102617446A (en) * | 2012-03-05 | 2012-08-01 | 西安近代化学研究所 | Synthesis method of 3, 5-N, N'-dicarbazoly benzene |
| CN103539819A (en) * | 2013-06-25 | 2014-01-29 | Tcl集团股份有限公司 | Bis-carbazolyl benzene compound, preparation method and application thereof and electroluminescent device |
Non-Patent Citations (1)
| Title |
|---|
| HONG HUANG等: "Optimizing the conjugation between N,N0-dicarbazolyl-3,5-benzene and triphenylphosphine oxide as bipolar hybrids for highly efficient blue and single emissive layer white phosphorescent OLEDs", 《ORGANIC ELECTRONICS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11812660B2 (en) | 2020-10-21 | 2023-11-07 | Wuhan Tianma Micro-Electronics Co., Ltd. | Organic compound, electroluminescent material and application thereof |
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