CN106800528B - A kind of naphthoquinones and 9,9,10,10- tetramethyl-anthracene class electroluminescent organic material and its preparation method and application - Google Patents

A kind of naphthoquinones and 9,9,10,10- tetramethyl-anthracene class electroluminescent organic material and its preparation method and application Download PDF

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CN106800528B
CN106800528B CN201611149861.1A CN201611149861A CN106800528B CN 106800528 B CN106800528 B CN 106800528B CN 201611149861 A CN201611149861 A CN 201611149861A CN 106800528 B CN106800528 B CN 106800528B
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naphthoquinones
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organic material
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CN106800528A (en
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李庆
胡葆华
石宇
王岩
邹广辉
潘峰
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Valiant Co Ltd
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Abstract

The invention discloses a kind of naphthoquinones and 9,9,10,10- tetramethyls-anthracene class electroluminescent organic material and its preparation method and application, above-mentioned electroluminescent organic material structural formula as shown in formula (i) or formula (ii):.Naphthoquinones provided by the invention and 9,9,10,10- tetramethyls-anthracene class electroluminescent organic material is applied in OLED luminescent device, so that the current efficiency of device, power efficiency and external quantum efficiency are greatly improved.Naphthoquinones provided by the invention and 9,9,10,10- tetramethyls-anthracene class electroluminescent organic material have good application effect, have good industrialization prospect.

Description

A kind of naphthoquinones and 9,9,10,10- tetramethyl-anthracene class electroluminescent organic material and its Preparation method and application
Technical field
The present invention relates to field of organic electroluminescent materials more particularly to a kind of naphthoquinones and 9,9,10,10- tetramethyls-anthracenes Class electroluminescent organic 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.
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 is prolonged Slow fluorescence (TADF) material is the third generation luminous organic material developed after organic fluorescence materials and organic phosphorescent material.It should Class material generally has small singlet-triplet poor (△ EST), and triplet excitons can be changed by anti-intersystem crossing It shines at singlet exciton.This can make full use of the singlet exciton and triplet excitons that are electrically excited lower formation, device it is interior Quantum efficiency can achieve 100%.Meanwhile material structure is controllable, and property is stablized, and it is cheap to be not necessarily to precious metal, in OLEDs Field has a extensive future.
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
For the above problem existing for existing OLED material, a kind of naphthoquinones and 9,9,10,10- tetramethyls-anthracene are now provided A kind of class electroluminescent organic material and its preparation method and application, it is desirable to provide organic electroluminescence hair with good photoelectric properties Luminescent material, to meet the requirement of panel manufacturing enterprise.
Specific technical solution is as follows:
The first aspect of the invention is to provide a kind of naphthoquinones and 9,9,10,10- tetramethyl-anthracene class organic electroluminescence material Material, has the feature that, for above-mentioned electroluminescent organic material with naphthoquinones and 9,9,10,10- tetramethyls-anthracene is mother nucleus structure, Its structural formula is as shown in formula (i) or formula (ii):
Wherein, Ar is selected from aromatic substituent group；
Wherein, R1Selected from containing substituent group or without substituent groupContaining substituent group or without substituent groupWherein, X1Selected from oxygen atom, sulphur atom, two (C1-10Straight chained alkyl) replace season alkyl (or tertiary alkyl), Two (C1-10Branched alkyl) the season alkyl (or tertiary alkyl), alkyl-substituted that replaces of the season alkyl (or tertiary alkyl), the aryl that replace One of the tertiary amine groups that tertiary amine groups or aryl replace.
Above-mentioned electroluminescent organic material, also has the feature that, containing substituent groupReplace with containing BaseFor in any phenyl ring or each phenyl ring by C6-20Aryl, Unitary replaces, wherein X2、X3、X4It is separately former selected from oxygen Son, sulphur atom, two (C1-10Straight chained alkyl) replace season alkyl (or tertiary alkyl), two (C1-10Branched alkyl) replace season alkyl In the tertiary amine groups that season alkyl (or tertiary alkyl), alkyl-substituted tertiary amine groups or the aryl that (or tertiary alkyl), aryl replace replace It is a kind of.
Above-mentioned electroluminescent organic material, also has the feature that, containing substituent groupWith contain substituent group 'sFor quilt in any phenyl ring or each phenyl ring Ortho position Unitary replaces, i.e., above-mentioned substituent group passes through C1-C2、C2-C3、C3-C4、C1'-C2'、C2'-C3'Or C3'-C4'Key connection.
Above-mentioned electroluminescent organic material, also has the feature that, Ar is selected from phenyl, C1-10What straight chained alkyl replaced Phenyl, C1-10One in phenyl, dibiphenylyl, terphenyl, naphthalene, anthryl, phenanthryl or benzo phenanthryl that branched alkyl replaces Kind.
Above-mentioned electroluminescent organic material, also has the feature that, X1、X2、X3And 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 Generation season alkyl, one of the tertiary amine groups that replace of methyl substituted tertiary amine groups or aryl.
Preferably, R in the present invention1It is preferably one of following:
Preferably, above-mentioned electroluminescent organic material is any one in following compound 1-153 in the present invention:
The above are some specific structure types, but naphthoquinones provided in the present invention and 9,9,10,10- tetramethyls-anthracene class Electroluminescent organic material is not limited to these listed chemical structures, and all based on formula (I) or formula (II), substituent group is The compound of the simple transformation of group should be all included in all ranges of definition.
The second aspect of the invention is to provide the preparation method of above-mentioned electroluminescent organic material, has such spy Sign, comprising:
1) preparation of formula (I) compound
Weighed 2- bromonaphthalene quinone and 9 are packed into reaction flask, reaction is added in 9,10,10- tetramethyls-anthracene, amine compound Solvent adds catalyst and alkali, under an inert atmosphere, by the mixed solution of above-mentioned reactant in 110-150 DEG C of reaction 10-24 Hour, it is chromatographed after stopping reaction through cooling, filtering, column, obtains electroluminescent organic material shown in formula (I), Chinese style of the present invention (I) synthesis of part of compounds shown in
2) preparation of formula (II) compound
Weighed naphthoquinones and 9 are packed into reaction flask, 9,10,10- tetramethyls-anthracene boronic acid compounds, bromo compound add Enter reaction dissolvent, adds catalyst and alkali, it is under an inert atmosphere, the mixed solution of above-mentioned reactant is anti-in 100-110 DEG C It answers 10-24 hours, is chromatographed after stopping reaction through cooling, filtering, column, obtain electroluminescent organic material shown in formula (II), this Part of compounds shown in invention Chinese style (II)
Preferably, in the preparation of formula (I) compound, 2- bromonaphthalene quinone and 9,9,10,10- tetramethyls-anthracene and-amine compound Molar ratio be 1:(1.0-1.5).
Preferably, in the preparation of formula (I) compound, catalyst is selected from Pd (OAc)2、P(t-Bu)3Or 1,2- dicyclohexyl One or more of phosphine -2', 6'- dimethoxy-biphenyl, preferably Pd (OAc)2With P (t-Bu)3, it is preferred that Pd (OAc)2With 2- bromonaphthalene quinone and 9, the molar ratio of 9,10,10- tetramethyls-anthracene are (0.005-0.01): 1, P (t-Bu)3With 2- bromonaphthalene quinone and 9, 9,10,10- tetramethyl-anthracene molar ratio is (0.01-0.02): 1.
Preferably, alkali is selected from one of sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, potassium methoxide or potassium carbonate, preferably uncle Sodium butoxide, also, sodium tert-butoxide and 2- bromonaphthalene quinone and 9, the molar ratio of 9,10,10- tetramethyls-anthracene are (2.0-4.0): 1.
Preferably, in the preparation of formula (II) compound, 9,10- dihydros -9,9,10,10- tetramethyls-anthracene boronic acid compounds with The molar ratio of bromo compound is 1:(1.0-1.5).
Preferably, catalyst is selected from Pd (OAc)2、P(t-Bu)3Or 1,2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl One or more of, preferably Pd (OAc)2With 1,2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl, also, Pd (OAc)2 With naphthoquinones and 9, the molar ratio of 9,10,10- tetramethyls-anthracene boronic acid compounds is (0.005-0.01): 1,2- dicyclohexyl phosphine- Simultaneously 9,9,10,10- tetramethyl-anthracene boronic acid compounds molar ratio is (0.01-0.02) for 2', 6'- dimethoxy-biphenyl and naphthoquinones: 1。
Preferably, alkali is selected from one of sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, potassium methoxide or potassium carbonate, preferably carbon Sour potassium, also, potassium carbonate and naphthoquinones and 9, the molar ratio of 9,10,10- tetramethyls-anthracene boronic acid compounds are (2.0-4.0): 1.
In above-mentioned preparation method, reaction dissolvent is selected from but is not limited to one of toluene, dimethylbenzene, mesitylene or several Kind.
It should be noted that those skilled in the art can should reasonably select based on the above technical solution, Measure solvent.
The third aspect of the invention is to provide above-mentioned electroluminescent organic material in preparing organic electroluminescence device Application.
The fourth aspect of the invention is to provide a kind of organic electroluminescence device, contains in the organic electroluminescence device Multiple functional layers, also have the feature that, at least one functional layer contains above-mentioned 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 (are related to naphthoquinones provided in the present invention and 9,9,10,10- tetramethyl-anthracene class organic electroluminescence material Material), electron transfer layer, electron injecting 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 Naphthoquinones and 9, electroluminescent ability possessed by 9,10,10- tetramethyls-anthracene class electroluminescent organic material, and be not to this The limitation of the application range of electroluminescent organic material provided by inventing.
The beneficial effect of above scheme is:
Simultaneously 9,9,10,10- tetramethyl-anthracene class electroluminescent organic material shines naphthoquinones provided by the invention applied to OLED In device, so that the current efficiency of device, power efficiency and external quantum efficiency are greatly improved.Naphthoquinones provided by the invention And 9,9,10,10- tetramethyls-anthracene class electroluminescent organic material has good application effect, before having good industrialization Scape.
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 Naphthoquinones and 9,9,10,10- tetramethyl-anthracene 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.
The preparation of 1 compound 1 of embodiment
0.012mol (2.00g) carbazole, 0.01mol is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250mL (4.45g) compound M1,0.03mol (2.88g) sodium tert-butoxide, 10-4mol (23mg) Pd (OAc) 2,2 × 10-4mol (0.4g) The toluene solution of P (t-Bu) 310%, 100mL toluene are heated to reflux 10 hours, sample contact plate, raw material fully reacting；Naturally cold But to room temperature (20-25 DEG C), filtering collects filtrate and carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), carries out column chromatography, obtain mesh Mark product, purity 99%, yield 63%.
Elemental analysis structure (molecular formula C38H29NO2): theoretical value C, 85.85；H,5.50；N,2.63；O, 6.02 test values: C,85.84；H,5.52；N,2.60；O,6.04.
HPLC-MS: materials theory value is 531.22, actual value 532.13.
The preparation of 2 compound 4 of embodiment
The preparation method is the same as that of Example 1 for compound 4, the difference is that replacing carbazole using raw material M2.
Elemental analysis structure (molecular formula C42H31NO2): theoretical value C, 86.72；H,5.37；N,2.41；O, 5.50 test values: C,86.70；H,5.38；N,2.42；O,5.50.
HPLC-MS: materials theory value is 581.23, actual value 582.20.
The preparation of 3 compound 8 of embodiment
0.012mol (3.09g) compound M3,0.01mol is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250mL (4.45g) compound M1,0.03mol (2.88g) sodium tert-butoxide, 10-4mol (23mg) Pd (OAc) 2,2 × 10-4mol (0.4g) The toluene solution of P (t-Bu) 310%, 100mL ortho-xylene are heated to reflux 10 hours, sample contact plate, raw material fully reacting；From It is so cooled to room temperature (20-25 DEG C), filters, collect filtrate and carry out vacuum rotary steam (- 0.09MPa, 110 DEG C), carry out column chromatography, obtain To target product, purity 99%, yield 52%.
Elemental analysis structure (molecular formula C44H31NO3): theoretical value C, 85.00；H,5.03；N,2.25；O, 7.72 test values: C,85.01；H,5.00；N,2.27；O,7.72.
HPLC-MS: materials theory value is 621.23, actual value 622.13.
The preparation of 4 compound 10 of embodiment
The preparation method of compound 10 is with embodiment 3, the difference is that replacing M3 using raw material M4.
Elemental analysis structure (molecular formula C47H37NO2): theoretical value C, 87.14；H,5.76；N,2.16；O, 4.94 test values: C,87.15；H,5.74；N,2.15；O,4.96.
HPLC-MS: materials theory value is 647.28, actual value 648.19.
The preparation of 5 compound 11 of embodiment
The preparation method of compound 11 is with embodiment 4, the difference is that replacing M3 using raw material M5.
Elemental analysis structure (molecular formula C50H36N2O2): theoretical value C, 86.18；H,5.21；N,4.02；O, 4.59 tests Value: C, 86.20；H,5.22；N,4.00；O,4.58.
HPLC-MS: materials theory value is 696.27, actual value 696.22.
The preparation of 6 compound 33 of embodiment
0.012mol (4.79g) compound M6,0.01mol is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250mL (4.45g) compound M1,0.03mol (2.88g) sodium tert-butoxide, 10-4mol (23mg) Pd (OAc) 2,2 × 10-4mol (0.4g) The toluene solution of P (t-Bu) 310%, 150mL mesitylene are heated to reflux 10 hours, sample contact plate, raw material fully reacting；From It is so cooled to room temperature (20-25 DEG C), filters, collect filtrate and carry out vacuum rotary steam (- 0.09MPa, 150 DEG C), carry out column chromatography, obtain To target product, purity 99%, yield 67%.
Elemental analysis structure (molecular formula C56H45NO2): theoretical value C, 88.04；H,5.94；N,1.83；O, 4.19 test values: C,88.03；H,5.97；N,1.82；O,4.18.
HPLC-MS: materials theory value is 763.34, actual value 762.40.
The preparation of 7 compound 45 of embodiment
The preparation method of compound 45 is with embodiment 6, the difference is that replacing M6 using raw material M7.
Elemental analysis structure (molecular formula C50H33NO4): theoretical value C, 84.37；H,4.67；N,1.97；O,8.99；Test Value: C, 84.35；H,4.66；N,2.00；O,8.99.
HPLC-MS: materials theory value is 711.24, actual value 712.24.
The preparation of 8 compound 54 of embodiment
The preparation method of compound 54 is with embodiment 6, the difference is that replacing M6 using raw material M8.
Elemental analysis structure (molecular formula C53H42N2O2): theoretical value C, 86.15；H,5.73；N,3.79；O,4.33；Test Value: C, 86.18；H,5.72；N,3.78；O,4.32.
HPLC-MS: materials theory value is 738.32, actual value 739.24.
The preparation of 9 compound 61 of embodiment
The preparation method of compound 61 is with embodiment 6, the difference is that replacing M6 using raw material M9.
Elemental analysis structure (molecular formula C53H42N2O2): theoretical value C, 86.15；H,5.73；N,3.79；O,4.33；Test Value: C, 86.16；H,5.72；N,3.77；O,4.35.
HPLC-MS: materials theory value is 738.32, actual value 739.33.
The preparation of 10 compound 65 of embodiment
The preparation method of compound 65 is with embodiment 6, the difference is that replacing M6 using raw material M10.
Elemental analysis structure (molecular formula C68H55N3O2): theoretical value C, 86.32；H,5.86；N,4.44；O,3.38；Test Value: C, 86.31；H,5.88；N,4.43；O,3.38.
HPLC-MS: materials theory value is 945.43, actual value 945.50.
The preparation of 11 compound 67 of embodiment
The preparation method of compound 67 is with embodiment 3, the difference is that 9- dimethyl acridinium replaces M3 using raw material 9.
Elemental analysis structure (molecular formula C41H35NO2): theoretical value C, 85.83；H,6.15；N,2.44；O,5.58；Test Value: C, 85.85；H,6.13；N,2.46；O,5.56.
HPLC-MS: materials theory value is 573.27, actual value 574.16
The preparation of 12 compound 69 of embodiment
The preparation method of compound 69 is with embodiment 3, the difference is that replacing M3 using raw material phenoxazine.
Elemental analysis structure (molecular formula C38H29NO3): theoretical value C, 83.34；H,5.34；N,2.56；O,8.76；Test Value: C, 83.35；H,5.33；N,2.55；O,8.77.
HPLC-MS: materials theory value is 547.21, actual value 548.22.
The preparation of 13 compound 70 of embodiment
The preparation method of compound 70 is with embodiment 3, the difference is that replacing M3 using raw material phenthazine.
Elemental analysis structure (molecular formula C38H29NO2S): theoretical value C, 80.97；H,5.19；N,2.48；O,5.68；S, 5.69；Test value: C, 80.96；H,5.20；N,2.45；O,5.67；S,5.72.
HPLC-MS: materials theory value is 563.19, actual value 564.11.
The preparation of 14 compound 79 of embodiment
The preparation method of compound 79 is with embodiment 3, the difference is that replacing M3 using raw material M11.
Elemental analysis structure (molecular formula C47H37NO2S): theoretical value C, 83.03；H,5.49；N,2.06；O,4.71；S, 4.72；Test value: C, 83.04；H,5.48；N,2.08；O,4.70；S,4.70.
HPLC-MS: materials theory value is 679.25, actual value 679.21.
The preparation of 15 compound 96 of embodiment
The preparation method of compound 96 is with embodiment 6, the difference is that replacing M6 using raw material M12.
Elemental analysis structure (molecular formula C53H42N2O2): theoretical value C, 86.15；H,5.73；N,3.79；O,4.33；Test Value: C, 86.14；H,5.72；N,3.80；O,4.33.
HPLC-MS: materials theory value is 738.32, actual value 738.29.
The preparation of 16 compound 115 of embodiment
The preparation method of compound 115 is with embodiment 6, the difference is that replacing M6 using raw material M13.
Elemental analysis structure (molecular formula C50H36N2O3): theoretical value C, 84.25；H,5.09；N,3.93；O,6.73；Test Value: C, 84.24；H,5.10；N,3.92；O,6.74.
HPLC-MS: materials theory value is 712.27, actual value 713.30.
The preparation of 17 compound 136 of embodiment
The preparation method of compound 136 is with embodiment 6, the difference is that replacing M6 using raw material M14.
Elemental analysis structure (molecular formula C46H33NO3): theoretical value C, 85.29；H,5.13；N,2.16；O,7.41；Test Value: C, 85.31；H,5.12；N,2.17；O,7.40.
HPLC-MS: materials theory value is 647.24, actual value 648.19.
The preparation of 18 compound 139 of embodiment
0.01mol (3.22g) 9- (4- bromophenyl)-carbazole is added under the atmosphere for being passed through nitrogen in the there-necked flask of 250mL, 0.01mol (4.12g) compound M1 boric acid, 0.03mol (4.14g) potassium carbonate, 10-4mol (23mg) Pd (OAc) 2,2 × 10- 4mol (84mg) 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl (S-phos), 100mL toluene, 100mL water.It is heated to reflux 10 hours, sample contact plate, raw material fully reacting；Cooled to room temperature (20-25 DEG C), liquid separation retain organic phase, filter, and receive Collect filtrate and carry out vacuum rotary steam (- 0.09MPa, 110 DEG C), carries out column chromatography, obtain target product, purity 99%, yield 78%.
Elemental analysis structure (molecular formula C44H33NO2): theoretical value C, 86.96；H,5.47；N,2.30；O,5.27；Test Value: C, 86.97；H,5.47；N,2.31；O,5.25.
HPLC-MS: materials theory value is 607.25, actual value 608.24.
The preparation of 19 compound 141 of embodiment
The preparation method is the same as that of Example 18 for compound 141, the difference is that replacing 9- (4- bromobenzene using raw material M15 Base)-carbazole.
Elemental analysis structure (molecular formula C53H41NO2): theoretical value C, 87.94；H,5.71；N,1.93；O,4.42；Test Value: C, 87.95；H,5.72；N,1.92；O,4.41.
HPLC-MS: materials theory value is 723.31, actual value 724.22.
The preparation of 20 compound 142 of embodiment
The preparation method is the same as that of Example 18 for compound 142, the difference is that replacing 9- (4- bromobenzene using raw material M16 Base)-carbazole.
Elemental analysis structure (molecular formula C56H40N2O2): theoretical value C, 87.02；H,5.22；N,3.62；O,4.14；Test Value: C, 87.04；H,5.19；N,3.63；O,4.14.
HPLC-MS: materials theory value is 772.31, actual value 773.24.
The preparation of 21 compound 146 of embodiment
The preparation method is the same as that of Example 18 for compound 146, the difference is that replacing 9- (4- bromobenzene using raw material M17 Base)-carbazole.
Elemental analysis structure (molecular formula C47H39NO2): theoretical value C, 86.87；H,6.05；N,2.16；O,4.92；Test Value: C, 86.88；H,6.07；N,2.14；O,4.91.
HPLC-MS: materials theory value is 649.29, actual value 650.33.
The hot property of the above-mentioned compound 2,146 and current material CBP prepared, luminescent spectrum and HOMO energy level Test result is as follows shown in table:
Compound Tg(℃) Td(℃) λPL(nm) Φ m (%) HOMO energy level (ev)
Compound 12 157 420 495 80.6 -5.85
Compound 146 150 414 500 78.6 -5.75
Material C BP 113 353 369 26.1 -5.9
By upper table data it is found that compound provided by the invention has suitable HOMO energy level and higher thermostabilization Property, it is suitable as the material of main part of luminescent layer；Meanwhile compound provided by the present invention has suitable luminescent spectrum and higher Φ m so that getting a promotion using compound provided by the present invention as the OLED device efficiency of dopant material and service life.
Organic electroluminescence device embodiment
Device 1-10 is prepared with the above-mentioned electroluminescent organic material in part in the embodiment of the present invention 22-31, it should Understand, device implementation process with as a result, be intended merely to preferably explain the present invention, not limitation of the present invention, above-mentioned organic Electroluminescent 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 140nm；
D) on the hole transport layer be deposited luminescent layer (compound provided by the invention: Ir (pq) 2acac=100:5 (wt: Wt), film thickness 30nm；
E) electron transfer layer (TPBI) is deposited on the light-emitting layer, film thickness 50nm；
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.
In the preparation method of above-mentioned organic electroluminescence device, the structural formula of TAPC, Ir (pq) 2acac, TPBI, CBP is such as Shown in lower:
As above after completing device 1-10 and comparative device, 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 1-10 and comparative device 1 As a result as shown in the table:
In above-mentioned test, using comparative example 1 as reference, 1 device performance indexes of comparative example is set as device detection performance 1.0.The current efficiency of comparative example 1 is 14.8cd/A (@10mA/cm2)；CIE chromaticity coordinates is (0.66,0.33)；Under 3000 brightness LT95 life time decay is 11Hr, and driving voltage is 4.5v (@10mA/cm2).Life-span test system be owner of the invention and The OLED device life-span tester of Shanghai University's joint development.
Device 11-16, device are prepared with the above-mentioned electroluminescent organic material in part in the embodiment of the present invention 32-37 The preparation process of 11-16 is identical as the preparation method of device 1-10, and difference is luminous layer structure difference, as above completes device After 11-16 and comparative device 2, anode and cathode is connected with well known driving circuit, the current efficiency of measurement device, is sent out The principal structural layer of the service life of light spectrum and device, device 11-16 and comparative device 2 and test result is as follows shown in table:
Embodiment Device Luminous layer structure (wt:wt) Current efficiency Color Driving voltage
32 11 CBP: compound 1=100:7 1.8 Green light 0.81
33 12 CBP: compound 11=100:7 2.2 Green light 0.70
34 13 CBP: compound 96=100:7 2.0 Green light 0.77
35 14 CBP: compound 141=100:7 1.5 Green light 0.90
36 15 CBP: compound 142=100:7 2.1 Green light 0.78
37 16 CBP: compound 146=100:7 1.4 Green light 0.72
Comparative example 2 Comparative device 2 CBP:GD19=100:7 1.0 Green light 1.0
Wherein, the structural formula of GD19 are as follows:
By upper table analysis it is found that no matter compound provided by the present invention is used as luminescent layer material of main part or adulterates material Material, the efficiency and starting voltage of obtained OLED luminescent device obtain larger change, especially device than known OLED material Efficiency roll-off under part high current density is improved.Simultaneously 9,9,10,10- tetramethyl-anthracene class has naphthoquinones provided by the present invention Electroluminescent material has good application effect in OLED luminescent device, has 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 (3)

1. a kind of naphthoquinones and 9,9,10,10- tetramethyls-anthracene class electroluminescent organic material, which is characterized in that the organic electroluminescence For luminescent material with naphthoquinones and 9,9,10,10- tetramethyls-anthracene is mother nucleus structure, structural formula as shown in formula (i) or formula (ii):
Wherein, Ar is selected from one of phenyl, naphthalene, anthryl, phenanthryl or benzo phenanthryl；
Wherein, R1Selected from containing substituent group or without substituent groupContaining substituent group or without substituent group
It is described containing substituent groupWith described containing substituent groupFor any phenyl ring or each phenyl ring quiltIt is condensed to replace,
Condensed site is the asterisk site of foregoing substituents, the X1, the X2, the X3With the X4Separately it is selected from oxygen Atom, sulphur atom, two (C1-10Straight chained alkyl) replace quaternary carbon, two (C1-10Branched alkyl) replace quaternary carbon, aryl replace season One of the tertiary amine groups that alkyl, methyl substituted tertiary amine groups or aryl replace.
2. a kind of naphthoquinones according to claim 1 simultaneously making by 9,9,10,10- tetramethyl-anthracene class electroluminescent organic material Have the application in organic electroluminescence devices.
3. a kind of organic electroluminescence device, including multiple functional layers, which is characterized in that at least one described functional layer contains Naphthoquinones described in claim 1 and 9,9,10,10- tetramethyl-anthracene class electroluminescent organic material.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0999256A1 (en) * 1998-05-01 2000-05-10 TDK Corporation Compounds for organic el element and organic el element
CN1747943A (en) * 2003-02-14 2006-03-15 出光兴产株式会社 Heteropolycyclic compound, and coloring matter, pigment, dye, color-changing material composition and color-changing film prepared therefrom
WO2011053035A2 (en) * 2009-11-02 2011-05-05 (주)씨에스엘쏠라 Organic light-emitting compound and an organic light-emitting element having the same
KR20120070468A (en) * 2010-12-21 2012-06-29 (주)씨에스엘쏠라 Organic light compound and organic light device using the same
WO2012093852A2 (en) * 2011-01-04 2012-07-12 주식회사 두산 Organic light emitting compound and organic electroluminescent device including same
KR101324787B1 (en) * 2011-05-19 2013-10-31 (주)씨에스엘쏠라 Organic light compound and organic light device using the same
TW201504392A (en) * 2013-06-21 2015-02-01 Univ Kyushu Nat Univ Corp Red light-emitting material, organic electroluminescence device and compound

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0999256A1 (en) * 1998-05-01 2000-05-10 TDK Corporation Compounds for organic el element and organic el element
CN1747943A (en) * 2003-02-14 2006-03-15 出光兴产株式会社 Heteropolycyclic compound, and coloring matter, pigment, dye, color-changing material composition and color-changing film prepared therefrom
WO2011053035A2 (en) * 2009-11-02 2011-05-05 (주)씨에스엘쏠라 Organic light-emitting compound and an organic light-emitting element having the same
KR20120070468A (en) * 2010-12-21 2012-06-29 (주)씨에스엘쏠라 Organic light compound and organic light device using the same
WO2012093852A2 (en) * 2011-01-04 2012-07-12 주식회사 두산 Organic light emitting compound and organic electroluminescent device including same
KR101324787B1 (en) * 2011-05-19 2013-10-31 (주)씨에스엘쏠라 Organic light compound and organic light device using the same
TW201504392A (en) * 2013-06-21 2015-02-01 Univ Kyushu Nat Univ Corp Red light-emitting material, organic electroluminescence device and compound

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