CN106800558B - A kind of titanium dioxide thioxanthene class electroluminescent organic material and its preparation method and application - Google Patents
A kind of titanium dioxide thioxanthene class electroluminescent organic material and its preparation method and application Download PDFInfo
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- CN106800558B CN106800558B CN201611247123.0A CN201611247123A CN106800558B CN 106800558 B CN106800558 B CN 106800558B CN 201611247123 A CN201611247123 A CN 201611247123A CN 106800558 B CN106800558 B CN 106800558B
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Abstract
The invention discloses a kind of titanium dioxide thioxanthene class electroluminescent organic material and its preparation method and application, the structural formula of above-mentioned titanium dioxide thioxanthene class electroluminescent organic material isIn titanium dioxide thioxanthene class electroluminescent organic material provided by the invention, using titanium dioxide thioxanthene as parent nucleus, connect aromatic heterocycle group, destroy molecular symmetry, to destroy the crystallinity of molecule, intermolecular aggtegation is avoided, the film forming having had, and be mostly rigid radical in molecule, thus improve the thermal stability of material；Simultaneously, titanium dioxide thioxanthene class electroluminescent organic material provided by the invention has D-A structure, electrons and holes distribution more balances, and there is suitable HOMO and lumo energy, high exciton utilization rate and high fluorescent radiation efficiency can be effectively improved, the efficiency roll-off under high current density is reduced, device voltage is reduced, improves device efficiency roll-off problem at higher current densities.
Description
Technical field
The present invention relates to electroluminescent organic material technical fields more particularly to a kind of titanium dioxide thioxanthene class organic electroluminescence to send out
Luminescent material and its preparation method and application.
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.
Currently, OLED display technology in smart phone, applied by the fields such as tablet computer, further will also be to electricity
Depending on etc. large scales application field extension, still with actual products application require compare, the luminous efficiency of OLED device, use
The performances such as service life also need further to be promoted.
Proposing high performance research for OLED luminescent device includes: the driving voltage for reducing device, improves shining for device
Efficiency improves the service life etc. of device.In order to realize OLED device performance continuous promotion, not only need from OLED device
The innovation of structure and manufacture craft is constantly studied and is innovated with greater need for oled light sulfate ferroelectric functional material, formulates out higher performance OLED
Functional material.
Oled light sulfate ferroelectric functional material applied to OLED device can be divided into two major classes, i.e. charge injection transmission from purposes
Material and luminescent material further can also inject charge into transmission material and be divided into electron injection transmission material, electronic blocking material
Luminescent material, can also be divided into main body luminescent material and dopant material by material, hole injection transmission material and hole barrier materials.
The different function film layer of industry application requirement and OLED device for current OLED device, the photoelectricity of device
Property requirements, it is necessary to which selection is more suitable for, and OLED functional material or combination of materials with high performance are just able to achieve the efficient of device
Rate, the overall characteristic of long-life and low-voltage.For current OLED shows the actual demand of Lighting Industry, OLED material at present
Development it is also far from enough, lag behind the requirement of panel manufacturing enterprise, the organic functions as material enterprise development higher performance
The exploitation of material is particularly important.
Summary of the invention
For the above problem existing for existing OLED material, a kind of titanium dioxide thioxanthene class organic electroluminescence material is now provided
Material and its preparation method and application, it is desirable to provide with good photoelectric properties, can satisfy the requirement of panel manufacturing enterprise
Titanium dioxide thioxanthene class electroluminescent organic material.
Specific technical solution is as follows:
The first aspect of the invention is to provide a kind of titanium dioxide thioxanthene class electroluminescent organic material, has such spy
Sign, above-mentioned electroluminescent organic material is using titanium dioxide thioxanthene as parent nucleus, shown in structural formula such as formula such as formula (I):
Wherein, Ar1、Ar2Separately it is selected from H ,-Ar3-(R1)nOr-R2, Ar3Selected from aromatic group, n takes 1 or 2；R1、
R2Separately selected from containing substituent group or without substituent groupContaining substituent group or without substituent groupX1Selected from oxygen atom, sulphur atom, selenium atom, two (C1-10Straight chained alkyl) season alkyl (or the tertiary alkane that replaces
Base), two (C1-10Branched alkyl) the season alkyl (or tertiary alkyl), the aryl that replace replace season alkyl (or tertiary alkyl), alkyl takes
One of the tertiary amine groups that the tertiary amine groups or aryl in generation replace.
Above-mentioned electroluminescent organic material, also has the feature that, contains substituent groupWith contain
Substituent groupFor quilt at least one phenyl ringOrOrtho position unitary
Replace, i.e., above-mentioned substituent group passes through C1-C2、C2-C3、C3-C4、C4-C5、C1'-C2'、C2'-C3'、C3'-C4'Or C4'-C5'Key connection,
Wherein, X2、X3、X4Separately it is selected from oxygen atom, sulphur atom, selenium atom, two (C1-10Straight chained alkyl) replace season alkyl
(or tertiary alkyl), two (C1-10Branched alkyl) replace season alkyl (or tertiary alkyl), aryl replace season alkyl (or tertiary alkyl),
One of the tertiary amine groups that alkyl-substituted tertiary amine groups or aryl replace.
Above-mentioned electroluminescent organic material, also has the feature that, contains substituent groupIn at least
Quilt on one phenyl ringReplace, andPass through C4-C5Or C4'-C5'When key connection, X1And X2Overlapping, only takes X1Or
Person X2。
Above-mentioned electroluminescent organic material, also has the feature that, X1、X2、X3、X4It is separately former selected from oxygen
Son, sulphur atom, selenium atom, two (C1-10Straight chained alkyl) replace quaternary carbon, two (C1-10Branched alkyl) replace quaternary carbon, aryl takes
One of the tertiary amine groups that the quaternary carbon in generation, alkyl-substituted tertiary amine groups or aryl replace.
Above-mentioned electroluminescent organic material, also has the feature that, Ar3Selected from phenyl, dibiphenylyl, terphenyl
One of base, naphthalene, anthryl or phenanthryl.
Preferably, R1、R2Separately selected from such as any one of flowering structure:
Preferably, electroluminescent organic material provided by the invention is preferably following A1-A24、B1-B23In any one:
The above are some specific structure types, but titanium dioxide thioxanthene class electroluminescent organic material provided in the present invention
It is not limited to these listed chemical structures, based on all (I) by formula, substituent group be the letter of group in all ranges defined
The monotropic compound changed should be all included.
The second aspect of the invention is to provide the preparation method of above-mentioned electroluminescent organic material, has such spy
Sign is packed into bromo compound, the amine compound of weighed titanium dioxide thioxanthene into reaction flask, and reaction dissolvent is added, adds
Catalyst, ligand and alkali, under an inert atmosphere, by the mixed solution of above-mentioned reactant in 95-100 DEG C reaction 10-24 hours, stop
It is chromatographed after only reacting through cooling, filtering, column, obtains electroluminescent organic material, synthetic route is as follows:
Above-mentioned preparation method, also has the feature that, the bromo compound of titanium dioxide thioxanthene and amine compound
Molar ratio is 1:1.0-4.0.
Above-mentioned preparation method, also has the feature that, catalyst Pd2(dba)3, also, catalyst and titanium dioxide
The molar ratio of the bromo compound of thioxanthene is 0.006-0.02:1；Ligand is tri-tert phosphorus, also, ligand and titanium dioxide thioxanthene
Bromo compound molar ratio be 0.006-0.02:1.
Above-mentioned preparation method, also has the feature that, alkali is sodium tert-butoxide, also, alkali is sodium tert-butoxide, alkali and two
The molar ratio for aoxidizing the bromo compound of thioxanthene is 1.0-6.0:1.
Above-mentioned preparation method, also has the feature that, reaction dissolvent is in toluene, benzene, dimethylbenzene
One kind.
It should be noted that those skilled in the art can should reasonably select simultaneously based on the above technical solution
Measure reaction dissolvent.
The third aspect of the invention is to provide above-mentioned titanium dioxide thioxanthene class electroluminescent organic material and is preparing Organic Electricity
Application in electroluminescence device.
The fourth aspect of the invention is to provide a kind of organic electroluminescence device, including multiple functional layers, also has this
The feature of sample, at least one functional layer contain above-mentioned titanium dioxide thioxanthene class electroluminescent organic material.
Prepared organic electroluminescence device generally comprises the ITO Conducting Glass being sequentially overlapped, sky in the present invention
Cave transport layer, luminescent layer (being related to titanium dioxide thioxanthene class electroluminescent organic material provided in the present invention), electron transfer layer, electricity
Sub- implanted layer (LiF) and cathode layer (Al), all functional layers are all made of vacuum evaporation process and are made.
It should be appreciated that making the purpose of OLED device in the present invention, it is intended merely to be better described, it is provided in the present invention
Electroluminescent ability possessed by titanium dioxide thioxanthene class electroluminescent organic material, and be not to provided by the present invention organic
The limitation of the application range of electroluminescent material.
The beneficial effect of above scheme is:
In titanium dioxide thioxanthene class electroluminescent organic material provided by the invention, using titanium dioxide thioxanthene as parent nucleus, connection virtue
Fragrant heterocyclic group, destroys molecular symmetry, to destroy the crystallinity of molecule, avoids intermolecular aggtegation, has
Good film forming, and be mostly rigid radical in molecule, thus improve the thermal stability of material；Meanwhile dioxy provided by the invention
Change thioxanthene class electroluminescent organic material have D-A structure, electrons and holes distribution more balances, and have suitable HOMO and
Lumo energy can effectively improve high exciton utilization rate and high fluorescent radiation efficiency, reduce the efficiency roll-off under high current density, drop
Low device voltage improves device efficiency roll-off problem at higher current densities；Have using titanium dioxide thioxanthene class provided by the invention
Current efficiency, power efficiency and the external quantum efficiency of the device of electroluminescent material, life-span upgrading are clearly.The present invention mentions
The titanium dioxide thioxanthene class electroluminescent organic material of confession has good application effect and industrialization prospect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of organic electroluminescence device provided in the embodiment of the present invention, by lower layer to upper layer,
It is followed successively by transparent substrate layer (1), transparent electrode layer (2), hole injection layer (3), hole transmission layer (4), luminescent layer (5), electronics
Transport layer (6), electron injecting layer (7), cathode reflection electrode layer (8), wherein luminescent layer (5) is related to provided in the present invention
Titanium dioxide thioxanthene class electroluminescent organic material.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art without creative labor it is obtained it is all its
His embodiment, shall fall within the protection scope of the present invention.
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.
The present invention will be further explained below with reference to the attached drawings and specific examples, but not as the limitation of the invention.
1 compound A1 of embodiment
0.01mol 9- phenyl -9- (4- bromophenyl) 10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.011mol compound C1,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.63%, yield 57%.
Elemental analysis structure (molecular formula C46H33NSO3): theoretical value: C, 81.27；H,4.89；N,2.06；O, 7.06 tests
Value: C, 81.39；H,4.90；N,2.36；O,7.40.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C46H33NSO3, theoretical value: 679.22, test value:
678.23。
2 compound A2 of embodiment
0.01mol 9- phenyl -9- (4- bromophenyl) 10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.011mol compound C2,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.46%, yield 52%.
Elemental analysis structure (molecular formula C46H33NO3S): theoretical value: C, 81.27；H,4.89；N,2.06；O,7.06；S,
4.72 test values: C, 81.02；H,4.75；N,2.18；O,7.19；S,4.62.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C46H33NO3S, theoretical value: 679.22, test value:
678.28。
3 compound A-13 of embodiment
0.01mol 9- phenyl -9- (4- bromophenyl) 10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.011mol compound C3,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.75%, yield 65%.
Elemental analysis structure (molecular formula C46H33NO3S): theoretical value: C, 81.27；H,4.89；N,2.06；O,7.06；S,
4.72 test values: C, 80.95；H,4.65；N,2.17；O,7.56；S,4.43.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C46H33NO3S, theoretical value: 679.22, test value:
678.66。
4 compound A4 of embodiment
0.01mol 9- phenyl -9- (4- bromophenyl) 10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.011mol compound C4,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.77%, yield 48%.
Elemental analysis structure (molecular formula C52H38N2O2S): theoretical value: C, 82.73；H,5.07；N,3.71；O,4.24；S,
4.25 test values: C, 82.33；H,4.87；N,3.92；O,4.10；S,4.11.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C52H38N2O2S, theoretical value: 754.27, test value:
754.34。
5 compound A-45 of embodiment
0.01mol 9- phenyl -9- (4- bromophenyl) 10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.011mol compound C5,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.35%, yield 47%.
Elemental analysis structure (molecular formula C56H37NO3S): theoretical value: C, 83.66；H,4.64；N,1.74；O,5.97；S,
3.99 test values: C, 81.53；H,5.67；N,1.54；O,6.21；S,4.85.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C56H37NO3S, theoretical value: 803.25, test value:
803.29。
6 compound A6 of embodiment
0.01mol 9- phenyl -9- (4- bromophenyl) 10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.011mol compound C6,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.44%, yield 60%.
Elemental analysis structure (molecular formula C49H32N2O3S): theoretical value: C, 80.75；H,4.43；N,3.84；O,6.59；S,
4.40 test values: C, 79.88；H,5.42；N,3.54；O,6.32；S,4.75.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C49H32N2O3S, theoretical value: 728.21, test value:
727.36。
7 compound A7 of embodiment
0.01mol 9- phenyl -9- (4- bromophenyl) 10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.011mol compound C7,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.57%, yield 62%.
Elemental analysis structure (molecular formula C49H32N2O3S): theoretical value: C, 80.75；H,4.43；N,3.84；O,6.59；S,
4.40 test values: C, 77.85；H,6.23；N,2.96；O,7.43；S,4.35.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C49H32N2O3S, theoretical value: 728.21, test value:
727.47。
8 compound A-28 of embodiment
0.01mol 9- phenyl -9- (4- bromophenyl) 10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.011mol compound C8,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.49%, yield 54%.
Elemental analysis structure (molecular formula C55H37N3O2S): theoretical value: C, 82.17；H,4.64；N,5.23；O,3.98；S,
3.99 test values: C, 81.98；H,5.44；N,5.45；O,3.53；S,3.12.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C55H37N3O2S, theoretical value: 803.26, test value:
803.61。
9 compound A9 of embodiment
0.01mol 9- phenyl -9- (4- bromophenyl) 10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.011mol compound C9,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.73%, yield 63%.
Elemental analysis structure (molecular formula C46H33NO3S): theoretical value: C, 81.27；H,4.89；N,2.06；O,7.06；S,
4.72 test values: C, 80.33；H,5.79；N,2.26；O,8.06；S,3.52.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C46H33NO3S, theoretical value: 679.22, test value:
679.47。
10 compound A10 of embodiment
0.01mol 9- phenyl -9- (4- bromophenyl) 10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.011mol compound C10,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-
4mol tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicon
Rubber column gel column obtains target product, purity 99.52%, yield 65%.
Elemental analysis structure (molecular formula C46H33NO4S): theoretical value: C, 79.40；H,4.78；N,2.01；O,9.20；S,
4.61 test values: C, 78.25；H,5.48；N,1.55；O,10.22；S,4.31.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C46H33NO4S, theoretical value: 695.21, test value:
695.25。
11 compound B-11 of embodiment
0.01mol 9,9- bis--(4- bromophenyl) -9H-10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.022mol compound C1,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2 (dba)3, 1 × 10-
4mol tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicon
Rubber column gel column obtains target product, purity 99.63%, yield 57%.
Elemental analysis structure (molecular formula C67H48N2O4S): theoretical value: C, 82.35；H,4.95；N,2.87；O,6.55；S,
3.28 test values: C, 82.38；H,4.94；N,2.86；O,6.54；S,3.28.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C46H33NSO3, theoretical value: 976.33, test value:
976.53。
12 compound B2 of embodiment
0.01mol 9,9- bis--(4- bromophenyl) -9H-10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.022mol compound C2,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.46%, yield 52%.
Elemental analysis structure (molecular formula C67H48N2O4S): theoretical value: C, 82.35；H,4.95；N,2.87；O,6.55；S,
3.28 test values: C, 82.40；H,4.95；N,2.84；O,6.58；S,3.23.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C67H48N2O4S), theoretical value: 976.33, test value:
976.58。
13 compound B3 of embodiment
0.01mol9,9- bis--(4- bromophenyl) -9H-10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.022mol compound C3,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.75%, yield 65%.
Elemental analysis structure (molecular formula C67H48N2O4S): theoretical value: C, 82.35；H,4.95；N,2.87；O,6.55；S,
3.28 test values: C, 82.42；H,4.98；N,2.81；O,6.58；S,3.21.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C67H48N2O4S), theoretical value: 976.33, test value:
976.36。
14 compound B4 of embodiment
0.01mol 9,9- bis--(4- bromophenyl) -9H-10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.022mol compound C4,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.77%, yield 48%.
Elemental analysis structure (molecular formula C79H58N4O2S): theoretical value: C, 84.16；H,5.19；N,4.97；O,2.84；S,
2.84 test values: C, 84.18；H,5.22；N,4.95；O,2.83；S,2.82.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C79H58N4O2S, theoretical value: 1126.43, test value:
1126.64。
15 compound B5 of embodiment
0.01mol 9,9- bis--(4- bromophenyl) -9H-10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.022mol compound C5,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.35%, yield 47%.
Elemental analysis structure (molecular formula C87H56N2O4S): theoretical value: C, 85.27；H,4.61；N,2.29；O,5.22；S,
2.62 test values: C, 85.36；H,4.60；N,2.24；O,5.23；S,2.57.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C87H56N2O4S, theoretical value: 1224.40, test value:
1224.46。
16 compound B-26 of embodiment
0.01mol 9,9- bis--(4- bromophenyl) -9H-10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.022mol compound C6,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.44%, yield 60%.
Elemental analysis structure (molecular formula C73H46N4O4S): theoretical value: C, 81.54；H,4.31；N,5.21；O,5.95；S,
2.98 test values: C, 81.63；H,4.26；N,5.20；O,5.99；S,2.92.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C73H46N4O4S, theoretical value: 1074.32, test value:
1074.39。
17 compound B7 of embodiment
0.01mol 9,9- bis--(4- bromophenyl) -9H-10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.022mol compound C7,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.57%, yield 62%.
Elemental analysis structure (molecular formula C73H46N4O4S): theoretical value: C, 81.54；H,4.31；N,5.21；O,5.95；S,
2.98 test values: C, 81.63；H,4.23；N,5.25；O,5.97；S,2.92.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C73H46N4O4S, theoretical value: 1074.32, test value:
1074.56。
18 compound B8 of embodiment
0.01mol 9,9- bis--(4- bromophenyl) -9H-10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.022mol compound C8,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.49%, yield 54%.
Elemental analysis structure (molecular formula C85H56N6O2S): theoretical value: C, 83.31；H,4.61；N,6.86；O,2.61；S,
2.62 test values: C, 83.35；H,4.55；N,6.84；O,2.60；S,2.66.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C85H56N6O2S, theoretical value: 1224.42, test value:
1224.51。
19 compound B9 of embodiment
0.01mol 9,9- bis--(4- bromophenyl) -9H-10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.022mol compound C9,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4mol
Tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicagel column,
Obtain target product, purity 99.73%, yield 63%.
Elemental analysis structure (molecular formula C67H48N2O4S): theoretical value: C, 82.35；H,4.95；N,2.87；O,6.55；S,
3.28 test values: C, 82.33；H,4.79；N,2.86；O,6.46；S,3.56.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C67H48N2O4S, theoretical value: 976.33, test value:
976.67。
20 compound B-11 0 of embodiment
0.01mol9,9- bis--(4- bromophenyl) -9H-10 is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250ml,
10- titanium dioxide thioxanthene, 0.022mol compound C10,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-
4mol tri-tert phosphorus, 150ml toluene are heated to reflux 24 hours, sample contact plate, and natural cooling filters, and filtrate revolving crosses silicon
Rubber column gel column obtains target product, purity 99.52%, yield 65%.
Elemental analysis structure (molecular formula C67H48N2O6S): theoretical value: C, 79.74；H,4.79；N,2.78；O,9.51；S,
3.18 test values: C, 79.76；H,4.74；N,2.71；O,9.57；S,3.22.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C67H48N2O6S, theoretical value: 1008.32, test value:
1008.35。
It is hot to compound A1, compound A2, compound B-11, compound B2, current material CBP, BD1 progress in the present invention
The test of energy, luminescent spectrum, fluorescence quantum efficiency and cyclic voltammetric stability, test result is as follows shown in table:
| Compound | Tg(℃) | Td(℃) | λPL(nm) | Φ f (%) | Cyclic voltammetric stability |
| Compound A1 | 122 | 379 | 451 | 77.5 | It is excellent |
| Compound B-11 | 132 | 382 | 472 | 79.5 | It is excellent |
| Material C BP | 113 | 353 | 369 | 26.1 | Difference |
| Compound A2 | 125 | 368 | 444 | 75.3 | It is excellent |
| Compound B2 | 134 | 377 | 461 | 77.3 | It is excellent |
| Material BD1 | - | 334 | 486 | 28.3 | Difference |
In above-mentioned test, by differential scanning calorimetry, (DSC, German Nai Chi company DSC204F1 show difference to glass transition temperature Tg
Scan calorimeter) measurement, 10 DEG C/min of heating rate；Thermal weight loss temperature Td is the temperature of the weightlessness 1% in nitrogen atmosphere, in day
It is measured on the TGA-50H thermogravimetric analyzer of this Shimadzu Corporation, nitrogen flow 20mL/min；λ PL is sample solution fluorescence
Launch wavelength is opened up general health SR-3 spectroradiometer using Japan and is measured；Φ f is that solid powder fluorescence quantum efficiency (utilizes beauty
The Maya2000Pro fiber spectrometer of state's marine optics, the C-701 integrating sphere and marine optics LLS-LED of Lan Fei company, the U.S.
The test solid fluorescence quantum efficiency test system of light source composition, reference literature (Adv.Mater.1997,9,230-232 side
Method is measured)；Cyclic voltammetric stability is identified by the redox characteristic of cyclic voltammetry test material；It surveys
Strip part: test sample is dissolved in the methylene chloride and acetonitrile mixed solvent that volume ratio is 2:1, concentration 1mg/mL, and electrolyte is
The tetrabutyl ammonium tetrafluoroborate of 0.1M or the organic solution of hexafluorophosphate.Reference electrode is Ag/Ag+ electrode, to electricity
Extremely titanium plate, working electrode are ITO electrode, and cycle-index is 20 times.
By upper table analysis it is found that the compounds of this invention has suitable luminescent spectrum, higher Φ f is suitable as shining
Layer material；Meanwhile the compounds of this invention has preferable oxidation-reduction stability, higher thermal stability, so that using this hair
The OLED device efficiency of bright compound and service life get a promotion.
Organic electroluminescence device embodiment
Device 1-8 is prepared with the above-mentioned electroluminescent organic material in part in the embodiment of the present invention 21-28, should be managed
Solution, device implementation process with as a result, being intended merely to preferably explain the present invention, not limitation of the present invention, above-mentioned Organic Electricity
Electroluminescence device the preparation method is as follows:
A) neutralizing treatment, pure water, drying are successively carried out to ito anode layer (film thickness 150nm), then carries out ultraviolet light-
Ozone washing is to remove the organic residue on 2 surface of transparent ITO-anode layer.
B) hole injection layer (MoO is deposited on ito anode layer3), film thickness 10nm；
C) hole transmission layer (TAPC) is deposited on hole injection layer, film thickness 80nm；
D) luminescent layer, film thickness 30nm are deposited on the hole transport layer；
E) electron transfer layer (TPBI) is deposited on the light-emitting layer, film thickness 40nm；
F) electron injecting layer device (LiF) is deposited on the electron transport layer, film thickness 1nm；
G) evaporation cathode reflection electrode layer (Al) on electron injecting layer, film thickness 80nm；
Wherein, the structural formula of each substance is as follows:
As above after completing device 1-9 and comparative device 1, anode and cathode is connected with well known driving circuit, is surveyed
The service life of the current efficiency of metering device, luminescent spectrum and device, the principal structural layer and test of device 1-9 and comparative device 1
As a result as shown in the table:
Wherein, the structural formula of GD19 are as follows:
Using comparative example 1 as reference in above-mentioned test, 1 device performance indexes of comparative example is set as 1.0.Comparative example 1
Current efficiency is 6.5cd/A (@10mA/cm2)；CIE chromaticity coordinates is (0.32,0.61)；LT95 life time decay is under 5000 brightness
3.8Hr。
Device 9-12, this hair are prepared with the above-mentioned electroluminescent organic material in part in the embodiment of the present invention 29-32
Bright middle embodiment 29-32 is identical as the manufacture craft of device in embodiment 21, and difference is luminous layer structure difference.
As above after completing device 9-12 and comparative device 2, anode and cathode is connected with well known driving circuit, is surveyed
The service life of the current efficiency of metering device, luminescent spectrum and device, the principal structural layer and test of device 1-9 and comparative device 2
As a result as shown in the table:
Wherein, the structural formula of BD1 are as follows:
By upper table analysis it is found that titanium dioxide thioxanthene class electroluminescent organic material provided by the invention is either as luminous
The material of main part of layer, or as the dopant material of luminescent layer, the current efficiency of device, service life are obtained than known OLED material
Efficiency roll-off under larger change, especially device high current density is improved.Compound of the present invention shines in OLED
There is good application effect in device, there is good industrialization prospect.
The foregoing is merely preferred embodiments of the present invention, are not intended to limit embodiments of the present invention and protection model
It encloses, to those skilled in the art, should can appreciate that all with made by description of the invention and diagramatic content
Equivalent replacement and obviously change obtained scheme, should all be included within the scope of the present invention.
Claims (7)
1. a kind of titanium dioxide thioxanthene class electroluminescent organic material, which is characterized in that the electroluminescent organic material is with dioxy
Change thioxanthene is parent nucleus, and structural formula is any one in following A1-A24, B1-B23:
2. a kind of preparation method of electroluminescent organic material according to claim 1, which is characterized in that into reaction flask
It is packed into bromo compound, the amine compound of titanium dioxide thioxanthene, reaction dissolvent is added, catalyst, ligand and alkali are added, lazy
Property atmosphere under, by the mixed solution of above-mentioned reactant in 95-100 DEG C reaction 10-24 hours, stop reaction after through cooling, filtering,
Column chromatography, obtains the electroluminescent organic material.
3. preparation method according to claim 2, which is characterized in that the bromo compound of the titanium dioxide thioxanthene with it is described
The molar ratio of amine compound is 1:1.0-4.0.
4. preparation method according to claim 2, which is characterized in that the catalyst is Pd2(dba)3, also, described urge
The molar ratio of the bromo compound of agent and the titanium dioxide thioxanthene is 0.006-0.02:1；The ligand is tri-tert phosphorus,
Also, the molar ratio of the bromo compound of the ligand and the titanium dioxide thioxanthene is 0.006-0.02:1.
5. preparation method according to claim 2, which is characterized in that the alkali is sodium tert-butoxide, also, the alkali and institute
The molar ratio for stating the bromo compound of titanium dioxide thioxanthene is 1.0-6.0:1.
6. a kind of titanium dioxide thioxanthene class electroluminescent organic material according to claim 1 is preparing organic electroluminescence
Application in part.
7. a kind of organic electroluminescence device, including multiple functional layers, which is characterized in that at least one described functional layer contains
Titanium dioxide thioxanthene class electroluminescent organic material described in claim 1.
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| CN104193736A (en) * | 2014-08-22 | 2014-12-10 | 华南理工大学 | Organic small molecular material based on spiro thioxanthene and organic photoelectric device using material as light emitting layer |
| CN104557856A (en) * | 2014-12-31 | 2015-04-29 | 南京邮电大学 | Preparation method for 9,9-diaryl thiophene xanthene-10,10-dioxide |
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| JP6521253B2 (en) * | 2013-07-03 | 2019-05-29 | 株式会社Ｋｙｕｌｕｘ | Luminescent material, delayed phosphor, organic light emitting device and compound |
| KR101520278B1 (en) * | 2014-07-01 | 2015-05-19 | 벽산페인트 주식회사 | The Host Compounds for Phosphorescent Emitter and Organic Light-Emitting Diodes Using This |
| KR101793448B1 (en) * | 2015-05-06 | 2017-11-03 | 벽산페인트 주식회사 | The Host Compounds for Phosphorescent Emitter and Organic Light-Emitting Diodes Using This |
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| CN104193736A (en) * | 2014-08-22 | 2014-12-10 | 华南理工大学 | Organic small molecular material based on spiro thioxanthene and organic photoelectric device using material as light emitting layer |
| CN104557856A (en) * | 2014-12-31 | 2015-04-29 | 南京邮电大学 | Preparation method for 9,9-diaryl thiophene xanthene-10,10-dioxide |
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