CN109575057A - A kind of boracic 6-membered heterocyclic compound and its application in organic electroluminescence device - Google Patents
A kind of boracic 6-membered heterocyclic compound and its application in organic electroluminescence device Download PDFInfo
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Abstract
The invention discloses a kind of boracic 6-membered heterocyclic compound and its application in organic electroluminescence device, the compound is using benzo hexatomic ring as core, on the centrally located hexatomic ring of boron element；The compound has the characteristics that intermolecular be not easy to crystallize, be not easy to assemble, have good filming.The compounds of this invention as organic electroluminescence device emitting layer material in use, device current efficiency, power efficiency and external quantum efficiency are greatly improved；Meanwhile device lifetime is promoted clearly.
Description
Technical field
The present invention relates to technical field of semiconductors, more particularly, to a kind of boracic organic compound, as well as shine
Application of the layer material on Organic Light Emitting Diode.
Background technique
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology can both be used to make
New display product is made, production novel illumination product is can be used for, is expected to substitute existing liquid crystal display and fluorescent lighting,
Application prospect is very extensive.
Structure of the OLED luminescent device like sandwich, including electrode material film layer, and be clipped in Different electrodes film layer it
Between organic functional material, various different function materials are overlapped mutually depending on the application collectively constitutes OLED luminescent device together.
As current device, when the two end electrodes application voltage to OLED luminescent device, and pass through electric field action organic layer functional material
Positive and negative charge in film layer, positive and negative charge is further compound in luminescent layer, i.e. generation OLED electroluminescent.
Application of the Organic Light Emitting Diode (OLEDs) in terms of large-area flat-plate is shown and is illuminated causes industry and
The extensive concern of art circle.However, traditional organic fluorescence materials can only be shone using 25% singlet exciton to be formed is electrically excited, device
The internal quantum efficiency of part is lower (up to 25%).External quantum efficiency is generally lower than 5%, and there are also very big with the efficiency of phosphorescent devices
Gap.Although phosphor material can efficiently use electricity since the strong SO coupling in heavy atom center enhances intersystem crossing
The singlet exciton formed and Triplet exciton are excited, makes the internal quantum efficiency of device up to 100%.But phosphor material exists
Expensive, stability of material is poor, and device efficiency tumbles the problems such as serious and limits it in the application of OLEDs.
Hot activation delayed fluorescence (TADF) material is the third developed after organic fluorescence materials and organic phosphorescent material
For luminous organic material.Such material generally has that small singlet-triplet is poor (△ EST), and triplet excitons can be with
It is transformed into singlet exciton by anti-intersystem crossing to shine.This can make full use of the singlet exciton for being electrically excited lower formation and three
Line state exciton, the internal quantum efficiency of device can achieve 100%.Meanwhile material structure is controllable, property is stablized, cheap nothing
Precious metal is needed, in having a extensive future for the field OLEDs.
Although theoretically 100% exciton utilization rate may be implemented in TADF material, following problem there are in fact: (1)
T1 the and S1 state for designing molecule has strong CT feature, very small S1-T1 state energy gap, although can realize by TADF process
High T1 → S1 state exciton conversion ratio, but low S1 state radiation transistion rate is also resulted in, consequently it is difficult to have both (or realizing simultaneously)
High exciton utilization rate and high fluorescent radiation efficiency；(2) even if having used doping device to mitigate T exciton concentration quenching effect, greatly
Efficiency roll-off is serious at higher current densities for the device of most TADF materials.
For current OLED shows the actual demand of Lighting Industry, the development of OLED material is also far from enough at present, falls
Afterwards in the requirement of panel manufacturing enterprise, the organic functional material as material enterprise development higher performance is particularly important.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, this application provides a kind of boracic 6-membered heterocyclic compound and its having
Application in organic electroluminescence devices.The compounds of this invention is based on TADF mechanism, is applied to organic electroluminescence as emitting layer material
Luminescent device, the device that the present invention makes have good photoelectric properties, can satisfy the requirement of panel manufacturing enterprise.
Technical scheme is as follows:
A kind of boracic 6-membered heterocyclic compound, shown in the structure of the compound such as general formula (1):
In general formula (1), X indicates oxygen atom or sulphur atom；
R1* substitution or unsubstituted C are expressed as6-30Aromatic radical or heteroaryl；
R2*-R5* expression hydrogen atom or C independently1-6Alkyl, C1-6Unsaturated alkyl, naphthenic base, replace or not
Substituted C6-30Aromatic radical or heteroaryl；Wherein R2*-R5*-Ar-R or-R, Ar table can also be independently expressed as
Show C6-20Arlydene；R2* with R3*、R3* with R4*、R4* with R5* can mutually be bonded to be formed cyclic structure or not mutually be bonded shape
Circlewise structure；
R6*-R9* expression hydrogen atom or C independently1-6Alkyl, naphthenic base, substitution or unsubstituted C6-30Fragrance
Base or heteroaryl, wherein R6* with R7*、R7* with R8*、R8* with R9* at least one set of bond is at structure shown in general formula (2)；
B is selected fromX1It is expressed as oxygen atom, sulphur atom, selenium atom, C1-10The alkylidene of linear or branched alkyl group substitution,
One of the tertiary amine groups that alkylidene, the alkyl or aryl of aryl substitution replace；
R, R ' independently be expressed as structure shown in hydrogen atom or general formula (3):
Wherein, R1、R2Structure shown in selection hydrogen or general formula (4) independently:
In general formula (4), a is selected fromOrX1、X2、X3, independently be expressed as oxygen atom, sulphur atom, C1-10
One of the tertiary amine groups that alkylidene, the alkyl or aryl of alkylidene, aryl substitution that linear or branched alkyl group replaces replace；
X is independent in general formula (3) is expressed as oxygen atom, sulphur atom, C1-10Alkylidene, the virtue of linear or branched alkyl group substitution
One of the tertiary amine groups that alkylidene, the alkyl or aryl of base substitution replace；
General formula (4) passes through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL‘1-CL’2Key, CL‘2-CL’3Key or CL‘3-CL’4Key with
The connection of structure shown in general formula (3).
The R2*-R5* at least one be expressed as-Ar-R or-R, Ar indicate C6-20Arlydene, R is expressed as general formula
(3) structure shown in；R6* with R7*、R7* with R8*、R8* with R9* at least one set of bond is at structure shown in general formula (2), formula of (2)
In R ' be expressed as hydrogen atom.
The R2* with R3*、R3* with R4*、R4* with R5* at least one set of mutually bond forms cyclic structure, R2*-R5* at least one
It is a be expressed as-Ar-R or-R, Ar indicate C6-20Arlydene, R is expressed as structure shown in general formula (3)；R6* with R7*、R7* with
R8*、R8* with R9* at least one set of bond at structure shown in general formula (2), the R ' in formula of (2) is expressed as hydrogen atom.
The R2* with R3*、R3* with R4*、R4* with R5* at least one set of mutually bond forms cyclic structure；R6* with R7*、R7*
With R8*、R8* with R9* at least one set of bond is at structure shown in general formula (2), and wherein R ' indicates structure shown in general formula (3), general formula (3)
In R1、R2Can independent expression hydrogen, methyl, isopropyl, tert-butyl, substitution or unsubstituted phenyl, substitution or do not take
Xenyl, substitution or the unsubstituted carbazyl in generation, substitution or unsubstituted dibenzofuran group, substitution or unsubstituted
9,9- dimethyl fluorenyl, substitution or unsubstituted acridinyl, substitution or unsubstituted diphenylacridine base, replace or
Unsubstituted phenoxazine base, substitution or unsubstituted phenothiazinyl.
Described R, R ' expression independently are as follows:
Any one of.The concrete structure formula of the compound are as follows:
Any one of.
A kind of organic electroluminescence device containing the boracic 6-membered heterocyclic compound, including luminescent layer, it is described to shine
Layer includes the boracic 6-membered heterocyclic compound.
The organic electroluminescence device further include transparent substrate layer, ito anode layer, hole injection layer, hole transmission layer,
Electronic barrier layer, hole barrier/electron transfer layer, electron injecting layer and cathode reflection electrode layer, the transparent substrate layer, ITO
Anode layer, hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole barrier/electron transfer layer, electron injecting layer
And cathode reflection electrode layer stacks gradually arrangement from bottom to up.
Above-mentioned hole injection layer can be MoO3(molybdenum trioxide), with a thickness of 10nm, the material of hole transport can be
TAPC, thickness can be 60nm；MCP is as material of main part, and the compounds of this invention is used as dopant material, in MCP
Adulterating mass percent can be 9%, and thickness can be 30nm；The material of electron-transport can be TPBI, and thickness can be
30nm；The material of the electron injecting layer can be LiF, and thickness can be 1nm；Cathode reflection electrode layer can be aluminium.
The present invention is beneficial to be had the technical effect that
It include the group of electron donor (donor, D) and electron acceptor (acceptor, A) in the compounds of this invention structural molecule
Conjunction can increase Orbital Overlap, improve luminous efficiency, while connect what aromatic heterocycle group was spatially separating to obtain HOMO, LUMO
Charge transfer state material, boracic heterocyclic system has strong electron attraction, so that between electron donor connected to it
Frontier orbit overlapping is smaller, realizes the energy level difference of small S1 state and T1 state, to alter between realizing inverse system under the conditions of thermostimulation
More；The boron-containing compound since D-A forms certain dihedral angle, while connecting other aromatic structures, can destroy molecule
Crystallinity avoids intermolecular aggtegation, the film forming and fluorescence quantum efficiency having had, and is suitable as luminescent layer doping
Materials'use；
Compound of the present invention can be used as luminescent layer dopant material and make applied to OLED luminescent device, obtain good
Device performance, the current efficiency of device, power efficiency and external quantum efficiency are greatly improved；Meanwhile for the device longevity
Life is promoted clearly.Compound-material of the present invention has good application effect in OLED luminescent device, has good
Good industrialization prospect.
Detailed description of the invention
Fig. 1 is the device architecture schematic diagram of the compounds of this invention application；Wherein, 1 is transparent substrate layer, and 2 be ito anode
Layer, 3 be hole injection layer, and 4 be hole transmission layer, and 5 be luminescent layer, and 6 be electron transfer layer, and 7 be electron injecting layer, and 8 be cathode
Reflection electrode layer；
Fig. 2 is the effect of visualization figure of the HOMO energy level of compound 5；Fig. 3 is the visualization effect of the lumo energy of compound 5
Fruit figure；Fig. 4 is the effect of visualization figure of the HOMO energy level of compound 10；Fig. 5 is the visualization effect of the lumo energy of compound 10
Fruit figure；Fig. 6 is the effect of visualization figure of the HOMO energy level of compound 91；Fig. 7 is the visualization effect of the lumo energy of compound 91
Fruit figure；Fig. 8 is the effect of visualization figure of the HOMO energy level of compound GD-19；Fig. 9 be compound GD-19 lumo energy can
Depending on changing effect picture.
Specific embodiment
The synthesis of 1 compound 5 of embodiment
The synthesis step of compound is as follows:
The three-necked flask of 150ml, be added 0.01mol 2, bis- bromofluoro benzene of 5-, 0.012mol M1,0.02mol sodium carbonate and
10ml glycol dimethyl ether, is passed through nitrogen protection, is heated to 190 degrees Celsius, is stirred to react 48 hours.It then cools to room temperature,
It pours into beaker, 50ml toluene is added and 50ml water stirs 20 minutes.Filtering, filtrate revolving, crosses silicagel column, obtains among white
Body 1a, purity 98.60%, yield 80.5%.HRMS (m/z): [M+H]+, theoretical value 523.06, measured value 523.10.
In 200ml three-necked flask, 0.01mol intermediate 1a and 50ml ether is added, stirring and dissolving leads to nitrogen, and system is cold
But to -10 DEG C, under nitrogen atmosphere, the lithium hexane solution of 0.02mol is slowly added dropwise, after instillation, is stirred to react
30 minutes；Then it is slowly dropped into the diethyl ether solution that 50ml contains C1 (0.01mol), is stirred to react 1 hour, is warming up to room temperature, stirs
Mix reaction 20 hours.Product is rotated, and 200ml toluene is added and 200ml water is diluted, and liquid separation removes water layer.It is organic
Layer is dried using anhydrous magnesium sulfate, is filtered and is rotated, and is crossed silicagel column, is obtained rice white intermediate 1b, purity
98.20%, yield 40.2%.HRMS (m/z): [M+H]+, theoretical value 577.40, measured value 577.32.
0.01mol 1b, 0.011mol compound D1 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 98.4%,
Yield 61.80%.HRMS (m/z): [M+H]+, theoretical value 795.87, measured value 795.81.
The synthesis of 2 compound 10 of embodiment
The synthesis step of compound is as follows:
0.01mol E1,0.012mol M1,0.02mol sodium carbonate and 10ml ethylene glycol is added in the three-necked flask of 150ml
Dimethyl ether is passed through nitrogen protection, is heated to 190 degrees Celsius, is stirred to react 48 hours.It then cools to room temperature, pours into beaker,
50ml toluene is added and 50ml water stirs 20 minutes.Filtering, filtrate revolving, crosses silicagel column, obtains white intermediate 2a, purity
97.60%, yield 65.8%.HRMS (m/z): [M+H]+, theoretical value 573.11, measured value 573.07.
In 200ml three-necked flask, 0.01mol intermediate 2a and 50ml ether is added, stirring and dissolving leads to nitrogen, and system is cold
But to -10 DEG C, under nitrogen atmosphere, the lithium hexane solution of 0.02mol is slowly added dropwise, after instillation, is stirred to react
30 minutes；Then it is slowly dropped into the diethyl ether solution that 50ml contains C1 (0.01mol), is stirred to react 1 hour, is warming up to room temperature, stirs
Mix reaction 20 hours.Product is rotated, and 200ml toluene is added and 200ml water is diluted, and liquid separation removes water layer.It is organic
Layer is dried using anhydrous magnesium sulfate, is filtered and is rotated, and is crossed silicagel column, is obtained rice white intermediate 2b, purity
98.40%, yield 36.4%.HRMS (m/z): [M+H]+, theoretical value 627.46, measured value 627.41.
0.01mol 2b, 0.011mol compound D1 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 99.0%,
Yield 59.7 0%.HRMS (m/z): [M+H]+, theoretical value 845.93, measured value 845.88.
The synthesis of 3 compound 20 of embodiment
The synthesis step of compound is as follows:
The three-necked flask of 150ml, be added 0.01mol 2, bis- bromofluoro benzene of 5-, 0.012mol M2,0.02mol sodium carbonate and
10ml glycol dimethyl ether, is passed through nitrogen protection, is heated to 190 degrees Celsius, is stirred to react 48 hours.It then cools to room temperature,
It pours into beaker, 50ml toluene is added and 50ml water stirs 20 minutes.Filtering, filtrate revolving, crosses silicagel column, obtains among white
Body 3a, purity 98.10%, yield 77.5%.HRMS (m/z): [M+H]+, theoretical value 496.89, measured value 496.84.
In 200ml three-necked flask, 0.01mol intermediate 3a and 50ml ether is added, stirring and dissolving leads to nitrogen, and system is cold
But to -10 DEG C, under nitrogen atmosphere, the lithium hexane solution of 0.02mol is slowly added dropwise, after instillation, is stirred to react
30 minutes；Then it is slowly dropped into the diethyl ether solution that 50ml contains C1 (0.01mol), is stirred to react 1 hour, is warming up to room temperature, stirs
Mix reaction 20 hours.Product is rotated, and 200ml toluene is added and 200ml water is diluted, and liquid separation removes water layer.It is organic
Layer is dried using anhydrous magnesium sulfate, is filtered and is rotated, and is crossed silicagel column, is obtained rice white intermediate 3b, purity
98.40%, yield 37.2%.HRMS (m/z): [M+H]+, theoretical value 551.33, measured value 551.36.
0.01mol 3b, 0.011mol compound D2 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 98.3%,
Yield 58.4%.HRMS (m/z): [M+H]+, theoretical value 795.87, measured value 795.84.
The synthesis of 4 compound 23 of embodiment
The synthesis step of compound is as follows:
0.01mol E1,0.012mol M2,0.02mol sodium carbonate and 10ml ethylene glycol is added in the three-necked flask of 150ml
Dimethyl ether is passed through nitrogen protection, is heated to 190 degrees Celsius, is stirred to react 48 hours.It then cools to room temperature, pours into beaker,
50ml toluene is added and 50ml water stirs 20 minutes.Filtering, filtrate revolving, crosses silicagel column, obtains white intermediate 4a, purity
98.30%, yield 74.5%.HRMS (m/z): [M+H]+, theoretical value 547.04, measured value 547.08.
In 200ml three-necked flask, 0.01mol intermediate 4a and 50ml ether is added, stirring and dissolving leads to nitrogen, and system is cold
But to -10 DEG C, under nitrogen atmosphere, the lithium hexane solution of 0.02mol is slowly added dropwise, after instillation, is stirred to react
30 minutes；Then it is slowly dropped into the diethyl ether solution that 50ml contains C1 (0.01mol), is stirred to react 1 hour, is warming up to room temperature, stirs
Mix reaction 20 hours.Product is rotated, and 200ml toluene is added and 200ml water is diluted, and liquid separation removes water layer.It is organic
Layer is dried using anhydrous magnesium sulfate, is filtered and is rotated, and is crossed silicagel column, is obtained rice white intermediate 4b, purity
98.70%, yield 36.4%.HRMS (m/z): [M+H]+, theoretical value 601.39, measured value 601.35.
0.01mol 4b, 0.011mol compound D3 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 98.8%,
Yield 62.1%.HRMS (m/z): [M+H]+, theoretical value 845.93, measured value 845.86.
The synthesis of 5 compound 33 of embodiment
The synthesis step of compound is as follows:
0.01mol 4b, 0.011mol compound D4 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 97.9%,
Yield 59.8 0%.HRMS (m/z): [M+H]+, theoretical value 894.97, measured value 894.91.
The synthesis of 6 compound 41 of embodiment
The synthesis step of compound is as follows:
0.01mol 4b, 0.011mol compound D5 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 98.7%,
Yield 62.5 0%.HRMS (m/z): [M+H]+, theoretical value 793.77, measured value 793.70.
The synthesis of 7 compound 50 of embodiment
The synthesis step of compound is as follows:
0.01mol 3b, 0.011mol compound D6 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 98.1%,
Yield 61.50%.HRMS (m/z): [M+H]+, theoretical value 796.79, measured value 796.80.
The synthesis of 8 compound 54 of embodiment
The synthesis step of compound is as follows:
The three-necked flask of 150ml, be added 0.01mol 2, bis- bromofluoro benzene of 5-, 0.012mol M3,0.02mol sodium carbonate and
10ml glycol dimethyl ether, is passed through nitrogen protection, is heated to 190 degrees Celsius, is stirred to react 48 hours.It then cools to room temperature,
It pours into beaker, 50ml toluene is added and 50ml water stirs 20 minutes.Filtering, filtrate revolving, crosses silicagel column, obtains among white
Body 5a, purity 98.40%, yield 63.5%.HRMS (m/z): [M+H]+, theoretical value 513.04, measured value 513.08.
In 200ml three-necked flask, 0.01mol intermediate 5a and 50ml ether is added, stirring and dissolving leads to nitrogen, and system is cold
But to -10 DEG C, under nitrogen atmosphere, the lithium hexane solution of 0.02mol is slowly added dropwise, after instillation, is stirred to react
30 minutes；Then it is slowly dropped into the diethyl ether solution that 50ml contains C1 (0.01mol), is stirred to react 1 hour, is warming up to room temperature, stirs
Mix reaction 20 hours.Product is rotated, and 200ml toluene is added and 200ml water is diluted, and liquid separation removes water layer.It is organic
Layer is dried using anhydrous magnesium sulfate, is filtered and is rotated, and is crossed silicagel column, is obtained rice white intermediate 5b, purity
98.0%, yield 34.5%.HRMS (m/z): [M+H]+, theoretical value 567.39, measured value 567.35.
0.01mol 5b, 0.011mol compound D7 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 99.0%,
Yield 658.7%.HRMS (m/z): [M+H]+, theoretical value 770.82, measured value 769.79.
The synthesis of 9 compound 73 of embodiment
The synthesis step of compound is as follows:
0.01mol 3b, 0.011mol compound D8 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 97.8%,
Yield 61.7%.HRMS (m/z): [M+H]+, theoretical value 844.91, measured value 844.86
The synthesis of 10 compound 91 of embodiment
The synthesis step of compound is as follows:
0.01mol 1b, 0.011mol compound D9 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 98.6%,
Yield 60.4%.HRMS (m/z): [M+H]+, theoretical value 795.87, measured value 795.79.
The synthesis of 11 compound 107 of embodiment
The synthesis step of compound is as follows:
0.01mol 4b, 0.011mol compound D10 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 98.4%,
Yield 66.7%.HRMS (m/z): [M+H]+, theoretical value 845.93, measured value 845.87.
The synthesis of 12 compound 127 of embodiment
The synthesis step of compound is as follows:
0.01mol 1b, 0.011mol compound D11 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 99.1%,
Yield 59.4%.HRMS (m/z): [M+H]+, theoretical value 795.87, measured value 795.84.
13 compound 136 of embodiment
The synthesis step of compound is as follows:
0.01mol 4b, 0.011mol compound D12 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 98.4%,
Yield 64.7%.HRMS (m/z): [M+H]+, theoretical value 819.85, measured value 819.80.
14 compound 141 of embodiment
The synthesis step of compound is as follows:
0.01mol 1b, 0.011mol compound D13 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, contact plate, fully reacting are sampled, natural cooling filters, and filtrate revolving crosses silicagel column, obtains target product, purity 98.1%.
Yield 62.1%.HRMS (m/z): [M+H]+, theoretical value 821.96, measured value 821.90.
The synthesis of 15 compound 155 of embodiment
The synthesis step of compound is as follows:
0.01mol 5b, 0.011mol compound D14 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 98.0%,
Yield 65.7%.HRMS (m/z): [M+H]+, theoretical value 985.11, measured value 85.07.
The synthesis of 16 compound 168 of embodiment
The synthesis step of compound is as follows:
The three-necked flask of 150ml, be added 0.01mol 2, bis- bromofluoro benzene of 5-, 0.012mol M4,0.02mol sodium carbonate and
10ml glycol dimethyl ether, is passed through nitrogen protection, is heated to 190 degrees Celsius, is stirred to react 48 hours.It then cools to room temperature,
It pours into beaker, 50ml toluene is added and 50ml water stirs 20 minutes.Filtering, filtrate revolving, crosses silicagel column, obtains among white
Body 6a, purity 98.20%, yield 61.9%.HRMS (m/z): [M+H]+, theoretical value 523.06, measured value 523.11.
In 200ml three-necked flask, 0.01mol intermediate 6a and 50ml ether is added, stirring and dissolving leads to nitrogen, and system is cold
But to -10 DEG C, under nitrogen atmosphere, the lithium hexane solution of 0.02mol is slowly added dropwise, after instillation, is stirred to react
30 minutes；Then it is slowly dropped into the diethyl ether solution that 50ml contains C1 (0.01mol), is stirred to react 1 hour, is warming up to room temperature, stirs
Mix reaction 20 hours.Product is rotated, and 200ml toluene is added and 200ml water is diluted, and liquid separation removes water layer.It is organic
Layer is dried using anhydrous magnesium sulfate, is filtered and is rotated, and is crossed silicagel column, is obtained rice white intermediate 6b, purity
98.6%, yield 40.1%.HRMS (m/z): [M+H]+, theoretical value 577.41, measured value 577.38.
0.01mol 6b, 0.011mol compound D15 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 99.2%,
Yield 62.7%.HRMS (m/z): [M+H]+, theoretical value 821.96, measured value 821.89.
The synthesis of 17 compound 203 of embodiment
The synthesis step of compound is as follows:
The three-necked flask of 150ml, be added 0.01mol 2, bis- bromofluoro benzene of 5-, 0.012mol M5,0.02mol sodium carbonate and
10ml glycol dimethyl ether, is passed through nitrogen protection, is heated to 190 degrees Celsius, is stirred to react 48 hours.It then cools to room temperature,
It pours into beaker, 50ml toluene is added and 50ml water stirs 20 minutes.Filtering, filtrate revolving, crosses silicagel column, obtains among white
Body 7a, purity 98.10%, yield 70.5%.HRMS (m/z): [M+H]+, theoretical value 496.98, measured value 496.95.
In 200ml three-necked flask, 0.01mol intermediate 7a and 50ml ether is added, stirring and dissolving leads to nitrogen, and system is cold
But to -10 DEG C, under nitrogen atmosphere, the lithium hexane solution of 0.02mol is slowly added dropwise, after instillation, is stirred to react
30 minutes；Then it is slowly dropped into the diethyl ether solution that 50ml contains C1 (0.01mol), is stirred to react 1 hour, is warming up to room temperature, stirs
Mix reaction 20 hours.Product is rotated, and 200ml toluene is added and 200ml water is diluted, and liquid separation removes water layer.It is organic
Layer is dried using anhydrous magnesium sulfate, is filtered and is rotated, and is crossed silicagel column, is obtained rice white intermediate 7b, purity
98.40%, yield 35.8%.HRMS (m/z): [M+H]+, theoretical value 551.33, measured value 551.28.
0.01mol 7b, 0.011mol compound D16 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 98.4%,
Yield 62.6%.HRMS (m/z): [M+H]+, theoretical value 769.79, measured value 769.76.
The synthesis of 18 compound 213 of embodiment
The synthesis step of compound is as follows:
0.01mol 4b, 0.011mol compound D17 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 98.4%,
Yield 61.4%.HRMS (m/z): [M+H]+, theoretical value 851.91, measured value 851.87.
The synthesis of 19 compound 242 of embodiment
The synthesis step of compound is as follows:
The three-necked flask of 150ml, be added 0.01mol 2, bis- bromofluoro benzene of 4-, 0.012mol M2,0.02mol sodium carbonate and
10ml glycol dimethyl ether, is passed through nitrogen protection, is heated to 190 degrees Celsius, is stirred to react 48 hours.It then cools to room temperature,
It pours into beaker, 50ml toluene is added and 50ml water stirs 20 minutes.Filtering, filtrate revolving, crosses silicagel column, obtains among white
Body 8a, purity 98.60%, yield 72.9%.HRMS (m/z): [M+H]+, theoretical value 496.98, measured value 496.95.
In 200ml three-necked flask, 0.01mol intermediate 8a and 50ml ether is added, stirring and dissolving leads to nitrogen, and system is cold
But to -10 DEG C, under nitrogen atmosphere, the lithium hexane solution of 0.02mol is slowly added dropwise, after instillation, is stirred to react
30 minutes；Then it is slowly dropped into the diethyl ether solution that 50ml contains C1 (0.01mol), is stirred to react 1 hour, is warming up to room temperature, stirs
Mix reaction 20 hours.Product is rotated, and 200ml toluene is added and 200ml water is diluted, and liquid separation removes water layer.It is organic
Layer is dried using anhydrous magnesium sulfate, is filtered and is rotated, and is crossed silicagel column, is obtained rice white intermediate 8b, purity
98.10%, yield 34.6%.HRMS (m/z): [M+H]+, theoretical value 551.33, measured value 551.29.
0.01mol 8b, 0.011mol compound D18 is added under the atmosphere for being passed through nitrogen in the four-hole bottle of 150ml,
0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, 50ml toluene, it is small to be heated to reflux 24
When, sampling contact plate, fully reacting, natural cooling, filtering, filtrate revolving crosses silicagel column, obtains target product, purity 98.1%,
Yield 64.7%.HRMS (m/z): [M+H]+, theoretical value 918.0, measured value 918.08.
The compounds of this invention can be used as the use of luminescent layer dopant material, to the compounds of this invention 5, compound 10, chemical combination
Object 20, compound 23, compound 33, compound 54, compound 73 and current material GD-19 carry out hot property, fluorescence volume respectively
The measurement of sub- efficiency, singlet-triplet poor (△ Est), testing result are as shown in table 1.
Table 1
| Compound | Td(℃) | PLQY | △Est(eV) | HOMO(eV) | Cyclic voltammetric stability |
| Compound 5 | 410 | 88 | 0.14 | -5.72 | It is excellent |
| Compound 10 | 406 | 87 | 0.10 | -5.70 | It is excellent |
| Compound 20 | 412 | 84 | 0.15 | -5.66 | It is excellent |
| Compound 23 | 421 | 82 | 0.17 | -5.70 | It is excellent |
| Compound 33 | 410 | 77 | 0.14 | -5.74 | It is excellent |
| Compound 54 | 398 | 74 | 0.18 | -5.70 | It is excellent |
| Compound 73 | 403 | 68 | 0.32 | -5.80 | It is excellent |
| GD-19 | 375 | 80 | 0.65 | -5.30 | Generally |
Note: thermal weight loss temperature Td is the temperature of the weightlessness 1% in nitrogen atmosphere, in the TGA-50H heat of Japanese Shimadzu Corporation
It is measured on weight analysis instrument, nitrogen flow 20mL/min；λPLIt is sample solution fluorescence emission wavelengths, opens up Pu Kang using Japan
The measurement of SR-3 spectroradiometer；Φ f is that solid powder fluorescence quantum efficiency (utilizes the Maya2000Pro of U.S.'s marine optics
Fiber spectrometer, the test solid fluorescence amount of C-701 integrating sphere and marine optics LLS-LED the light source composition of Lan Fei company, the U.S.
Sub- efficiency test system, reference literature Adv.Mater.1997,9,230-232 method are measured)；Cyclic voltammetric stability
It is that the redox characteristic of material is observed by cyclic voltammetry to be identified；Test condition: test sample is dissolved in volume ratio
For the methylene chloride and acetonitrile mixed solvent of 2:1, concentration 1mg/mL, electrolyte is the tetrabutyl ammonium tetrafluoroborate or hexafluoro of 0.1M
The organic solution of phosphoric acid tetrabutylammonium.Reference electrode is Ag/Ag+ electrode, is titanium plate to electrode, working electrode is ITO electrode, is followed
Ring number is 20 times.
By upper table data it is found that the compounds of this invention thermal stability with higher, lesser singlet-triplet
Difference, higher Φ f, so that getting a promotion using the compounds of this invention as the OLED device efficiency of dopant material and service life.
MCP is steamed as material of main part, the compounds of this invention as doped luminescent material (doping mass concentration is 9%) altogether
It is fabricated to organic film.It is excited with the ultraviolet light of 365nm, measurement organic film fluorescence intensity is led to test angle distribution situation
It crosses optics fitting software and measures its anisotropy factor α.α is smaller, shows that the luminous subconstiuent of the level of organic film dopant material is got over
More, the utilization rate of dopant material radioluminescence is higher.As TADF material (thermal excitation delayed fluorescence material), the longevity of delayed fluorescence
Life is shorter, and triplet state is easy to return singlet by transition between anti-gap, is quenched so as to avoid triplet state, is able to ascend the effect of device
Rate and service life.The results are shown in Table 2.
Table 2
Note: organic film carries out double source by ANS evaporated device and steams altogether, and vapor deposition substrate is high saturating quartz glass, and object is mixed
Impurity level concentration is 8%.After vapor deposition, (concentration of water and oxygen be less than 1ppm) is packaged in glove box.Sample is logical
Superrefraction rate matching fluid is placed in molten silicon semicolumn prism, changes light emitting angle by turntable, spectrum test uses
Sphere Optics SMS-500 type spectrometer.The delayed fluorescence service life is tested by the FLS980 transient lifetime of Edinburg instrument
Instrument obtains.
As can be seen from Table 2 relative to Traditional dopant material GD-19, the sub- anisotropy factor that shines of the compounds of this invention
It is small, therefore the light extraction efficiency of organic layer can be improved, promote OLED device efficiency.Meanwhile triplet state can be efficiently used and swashed
The energy of son improves device efficiency.
Calculate by HOMO, lumo energy of the quantum-mechanical effects software ORCA to the compounds of this invention and go forward side by side
Row visualization, calculation method use B3LYP hydridization functional, base group 6-31g (d).HOMO effect of visualization such as Fig. 2 of compound 5
It is shown；The LUMO effect of visualization of compound 5 is as shown in Figure 3；The HOMO effect of visualization of compound 10 is as shown in figure 4, chemical combination
The LUMO effect of visualization of object 10 is as shown in Figure 5；The HOMO effect of visualization of compound 91 is as shown in fig. 6, compound 91
LUMO effect of visualization is as shown in Figure 7；The HOMO effect of visualization of compound GD-19 is as shown in figure 8, compound GD-19
HOMO effect of visualization is as schemed, shown in 9.
It can be seen greatly from the spatial distribution of HOMO, LUMO in the molecule, at the HOMO and lumo energy of the compounds of this invention
In the state that is spatially separating, HOMO, LUMO degree of overlapping are small, small so as to cause singlet-triplet difference, are conducive to triplet state and swash
Son is converted into singlet exciton by thermal excitation, theoretically device internal quantum efficiency can be made to reach 100%.
20-38 and comparative example 1 compound that the present invention will be described in detail synthesizes are in the devices as hair by the following examples
The application effect of photosphere dopant material.For embodiment 20-38 compared with comparative example 1, the manufacture craft of the device is identical, and
And identical baseplate material and electrode material are used, the film thickness of electrode material is also consistent, except that in device
Emitting layer material is changed, using the compounds of this invention.The structure composition of each embodiment obtained device such as 3 institute of table
Show.The performance test results of each device are as shown in table 4.
2/ hole injection layer of embodiment 20:ITO anode layer, 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4
(TAPC, thickness 60nm)/luminescent layer 5 (the weight ratio blending of MCP and compound 18 according to 100:9, thickness 40nm))/electronics biography
Defeated 6 (TPBI, thickness 30nm)/electron injecting layer of layer, 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).The molecule of each compound
Structural formula is as follows:
Specific preparation process is as follows: transparent substrate layer 1 uses transparent material, such as glass；To ito anode layer 2, (film thickness is
It 150nm) is washed, i.e., carries out ultraviolet-ozone washing again after successively carrying out neutralizing treatment, pure water, drying to remove
The organic residue on the bright surface ITO.On having carried out the ito anode layer 2 after above-mentioned washing, using vacuum deposition apparatus, steam
Plate the molybdenum trioxide MoO that film thickness is 10nm3It is used as hole injection layer 3.And then the TAPC of 60nm thickness is deposited as empty
Cave transport layer 4.After above-mentioned hole mobile material vapor deposition, the luminescent layer 5 of OLED luminescent device is made, structure includes OLED
For the used material MCP of luminescent layer 5 as material of main part, compound 10 is used as dopant material, and dopant material doping ratio is 9% weight
Ratio is measured, luminescent layer film thickness is 40nm.After above-mentioned luminescent layer 5, continuation vacuum evaporation electron transport layer materials are TPBI, the material
The vacuum evaporation film thickness of material is 30nm, this layer is electron transfer layer 6.On electron transfer layer 6, pass through vacuum deposition apparatus, system
Make lithium fluoride (LiF) layer that film thickness is 1nm, this layer is electron injecting layer 7.On electron injecting layer 7, filled by vacuum evaporation
It sets, aluminium (Al) layer that production film thickness is 80nm, this layer is the use of cathode reflection electrode layer 8.OLED is completed as described above to shine
After device, anode and cathode is connected with well known driving circuit, the luminous efficiency of measurement device, luminescent spectrum and device
The I-E characteristic of part.
Table 3
Table 4
Note: for device detection performance using comparative example 1 as reference, 1 device performance indexes of comparative example is set as 1.0.Compare
The external quantum efficiency of example 1 is 4.0% (@3000cd/m2)；Driving service life (light emission luminance be original intensity 90%) is 200
Hour.Life-span test system is the OLED device life-span tester of owner of the invention and Shanghai University's joint development.
Compound of the present invention can shine as luminescent layer dopant material using with OLED from the results shown in Table 4
Element manufacturing, and compared with comparative example 1, either efficiency or service life obtain larger improvement than known OLED material, special
It is not the biggish promotion of efficiency acquisition of device.
Although disclosing the present invention by embodiment and preferred embodiment, it should be appreciated that it is public that the present invention is not limited to institutes
The embodiment opened.On the contrary, it will be understood by those skilled in the art that it is intended to various modifications and similar arrangement.Therefore, institute
Attached the scope of the claims should be consistent with widest explanation to cover all such modifications and similar arrangement.
Claims (8)
1. a kind of boracic 6-membered heterocyclic compound, it is characterised in that shown in the structure of the compound such as general formula (1):
In general formula (1), X indicates oxygen atom or sulphur atom；
R1* substitution or unsubstituted C are expressed as6-30Aromatic radical or heteroaryl；
R2*-R5* expression hydrogen atom or C independently1-6Alkyl, C1-6Unsaturated alkyl, naphthenic base replace or unsubstituted
C6-30Aromatic radical or heteroaryl；Wherein R2*-R5* can also independently be expressed as-Ar-R or-R, Ar indicate
C6-20Arlydene；R2* with R3*、R3* with R4*、R4* with R5* it can mutually be bonded to form cyclic structure or not mutually bond formation
Cyclic structure；
R6*-R9* expression hydrogen atom or C independently1-6Alkyl, naphthenic base, substitution or unsubstituted C6-30Aromatic radical or
Person's heteroaryl, wherein R6* with R7*、R7* with R8*、R8* with R9* at least one set of bond is at structure shown in general formula (2)；
B is selected fromX1It is expressed as oxygen atom, sulphur atom, selenium atom, C1-10Alkylidene, the aryl of linear or branched alkyl group substitution
One of the tertiary amine groups that substituted alkylidene, alkyl or aryl replace；
R, R ' independently be expressed as structure shown in hydrogen atom or general formula (3):
Wherein, R1、R2Structure shown in selection hydrogen or general formula (4) independently:
In general formula (4), a is selected fromX1、X2、X3, independently be expressed as oxygen atom, sulphur atom, C1-10Directly
One of the tertiary amine groups that alkylidene, the alkyl or aryl of alkylidene, aryl substitution that chain or branched alkyl replace replace；
X is independent in general formula (3) is expressed as oxygen atom, sulphur atom, C1-10Alkylidene, the aryl of linear or branched alkyl group substitution take
One of the tertiary amine groups that alkylidene, the alkyl or aryl in generation replace；
General formula (4) passes through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL‘1-CL’2Key, CL‘2-CL’3Key or CL‘3-CL’4Key and general formula
(3) connection of structure shown in.
2. boracic 6-membered heterocyclic compound according to claim 1, it is characterised in that the R2*-R5* at least one table
Be shown as-Ar-R or-R, Ar indicate C6-20Arlydene, R is expressed as structure shown in general formula (3)；R6* with R7*、R7* with R8*、
R8* with R9* at least one set of bond at structure shown in general formula (2), the R ' in formula of (2) is expressed as hydrogen atom.
3. boracic 6-membered heterocyclic compound according to claim 1, it is characterised in that the R2* with R3*、R3* with R4*、R4*
With R5* at least one set of mutually bond forms cyclic structure, R2*-R5* at least one be expressed as-Ar-R or-R, Ar indicate C6-20
Arlydene, R is expressed as structure shown in general formula (3)；R6* with R7*、R7* with R8*、R8* with R9* at least one set of bond is at general formula (2)
Shown structure, the R ' in formula of (2) are expressed as hydrogen atom.
4. boracic 6-membered heterocyclic compound according to claim 1, it is characterised in that the R2* with R3*、R3* with R4*、R4*
With R5* at least one set of mutually bond forms cyclic structure；R6* with R7*、R7* with R8*、R8* with R9* at least one set of bond is at general formula
(2) structure shown in, wherein R ' indicates structure shown in general formula (3), the R in general formula (3)1、R2It can independent expression hydrogen, methyl, different
Propyl, tert-butyl, substitution or unsubstituted phenyl, substitution or unsubstituted xenyl, substitution or unsubstituted carbazole
Base, substitution or unsubstituted dibenzofuran group, substitution or unsubstituted 9,9- dimethyl fluorenyl, substitution or unsubstituted
Acridinyl, substitution or unsubstituted diphenylacridine base, substitution or unsubstituted phenoxazine base, substitution or unsubstituted
Phenothiazinyl.
5. boracic 6-membered heterocyclic compound according to claim 1, it is characterised in that described R, R ' expression independently
Are as follows:
Any one of.
6. boracic 6-membered heterocyclic compound according to claim 1, it is characterised in that the concrete structure formula of the compound are as follows:
Any one of.
7. a kind of organic electroluminescence device containing boracic 6-membered heterocyclic compound described in claim 1, including luminescent layer,
It is characterized in that the luminescent layer includes the boracic 6-membered heterocyclic compound.
8. organic electroluminescence device according to claim 7, it is characterised in that the organic electroluminescence device also wraps
Include transparent substrate layer, ito anode layer, hole injection layer, hole transmission layer, electronic barrier layer, hole barrier/electron transfer layer,
Electron injecting layer and cathode reflection electrode layer, the transparent substrate layer, ito anode layer, hole injection layer, hole transmission layer, electricity
Sub- barrier layer, luminescent layer, hole barrier/electron transfer layer, electron injecting layer and cathode reflection electrode layer successively layer from bottom to up
Laying up is set.
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| CN110272440A (en) * | 2018-03-15 | 2019-09-24 | 江苏三月光电科技有限公司 | A kind of boracic 6-membered heterocyclic compound and its application in organic electroluminescence device |
| CN112409392A (en) * | 2020-11-27 | 2021-02-26 | 上海天马有机发光显示技术有限公司 | Compound, display panel and display device |
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