CN106467497A - A kind of compound with anthrone as core and its application in OLED - Google Patents

A kind of compound with anthrone as core and its application in OLED Download PDF

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Publication number
CN106467497A
CN106467497A CN201610684979.8A CN201610684979A CN106467497A CN 106467497 A CN106467497 A CN 106467497A CN 201610684979 A CN201610684979 A CN 201610684979A CN 106467497 A CN106467497 A CN 106467497A
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formula
compound
anthrone
core
straight
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CN106467497B (en
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陈棪
李崇
徐凯
张兆超
叶中华
张小庆
王立春
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Jiangsu Sunera Technology Co Ltd
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Jiangsu Sanyue Optoelectronic Technology Co Ltd
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Priority to PCT/CN2017/097613 priority patent/WO2018033085A1/en
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Abstract

The invention discloses a kind of compound with anthrone as core and its application in organic electroluminescence device, this compound is with anthrone as parent nucleus, connect aromatic heterocycle group, destroy molecular symmetry, thus the crystallinity of saboteur, avoid intermolecular aggregation, the film property having had.The compounds of this invention is applied on Organic Light Emitting Diode as emitting layer material, the OLED of application the compounds of this invention has good photoelectric properties, disclosure satisfy that the requirement of panel manufacturing enterprise.

Description

A kind of compound with anthrone as core and its application in OLED
Technical field
The present invention relates to technical field of semiconductors, especially relate to a kind of compound based on anthrone, and its as send out Application on Organic Light Emitting Diode for the light layer material.
Background technology
Organic Light Emitting Diode (OLED:Organic Light Emission Diodes) become very popular both at home and abroad Emerging flat faced display product, this is because when OLED display has self-luminous, wide viewing angle (reaching more than 175 °), short reaction Between, high-luminous-efficiency, wide colour gamut, low-work voltage (3～10V), panel thin (being smaller than 1mm) and the characteristic such as rollable.OLED It is called star's flat display products of 21 century.More and more ripe with technology, it is possible to be developed rapidly from now on, front Limitless on the way.
The principle that OLED lights is by applying an applied voltage, after hole and electronics overcome interface energy barrier, by anode With negative electrode injection, the LUMO of the HOMO energy rank and electron transfer layer that respectively enter hole-transporting layer can rank；Then electric charge is additional It is transferred to the interface of hole-transporting layer and electron transfer layer, the energy jump at interface make interface have electric charge under the driving of electric field Accumulation；Electronics, hole in the organic substance having the characteristics of luminescence in conjunction with, formed an exciton, this exciton is in general ring Border is unstable, returns to stable ground state by releasing energy in the form of light or heat afterwards.Via electronics, hole in conjunction with The excited state producing only 25% is singlet excited in theory, and remaining 75% is triplet excited state, by with the shape of phosphorescence or heat Formula revert to ground state.
Organic Light Emitting Diode (OLEDs) large-area flat-plate show and illumination in terms of application cause industrial quarters and The extensive concern of art circle.However, traditional organic fluorescence materials can only be lighted using 25% singlet exciton being electrically excited formation, device The internal quantum efficiency of part is relatively low (being up to 25%).External quantum efficiency is generally less than 5%, also very big with the efficiency of phosphorescent devices Gap.Although phosphor material enhances intersystem crossing due to the strong SO coupling in heavy atom center, can with effectively utilizes electricity Excite singlet exciton and the Triplet exciton of formation, make the internal quantum efficiency of device reach 100%.But phosphor material exists Expensive, stability of material is poor, limits its application in OLEDs the problems such as device efficiency tumbles serious.Hot activation is prolonged Fluorescence (TADF) material is the third generation luminous organic material of development after organic fluorescence materials and organic phosphorescent material late.Should Class material typically has poor (the △ E of little singletstate-tripletST), triplet excitons can be changed by anti-intersystem crossing Singlet exciton is become to light.This can make full use of the singlet exciton being electrically excited lower formation and triplet excitons, device interior Quantum efficiency can reach 100%.Meanwhile, material structure is controlled, stable in properties, low price without precious metal, in OLEDs The having a extensive future of field.
Although TADF material can realize 100% exciton utilization rate in theory, there are in fact following problem：(1) T1 the and S1 state of design molecule has strong CT feature, and very little S1-T1 state energy gap is although can be realized by TADF process High T1→S1State exciton conversion ratio, but also result in low S1 state radiation transistion speed, consequently it is difficult to have (or realizing) concurrently simultaneously High exciton utilization rate and high fluorescent radiation efficiency；(2) even if having adopted 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 the actual demand that current OLED shows Lighting Industry, the development of current OLED material is also far from enough, falls After the requirement of panel manufacturing enterprise, the organic functional material as material enterprise development higher performance is particularly important.
Content of the invention
For prior art exist the problems referred to above, the applicant provide a kind of compound based on anthrone and its Application in OLED.The present invention is applied to organic light emission based on the anthracene ketone compounds of TADF mechanism as emitting layer material On diode, the OLED of application the compounds of this invention has good photoelectric properties, disclosure satisfy that panel manufacturing enterprise Require.
Technical scheme is as follows：
The applicant provides a kind of compound with anthrone as core, shown in the structure such as formula (1) of described compound：
In formula (1), D1、D2Selection C independently1-10One of straight or branched alkyl or phenyl, D1、D2 Can be identical or different；Ar representsOr；Wherein, Ar1Represent phenyl, dibiphenylyl, terphenyl, Naphthyl, anthryl or phenanthryl；M, n selection 1 or 2 independently；
DescribedRepresent (Ar)mIt is connected on any carbon atom on the phenyl ring of formula (1) both sides；
R adopts formula (2), formula (3), formula (4) or formula (5) to represent：
Wherein,
X1, Y be oxygen atom, sulphur atom, selenium atom, C1-10The Asia that the alkylidene of straight or branched alkyl replacement, aryl replace One of tertiary amine groups that alkyl, alkyl or aryl replace；
R1Choose structure shown in formula (6), R2Choose structure shown in formula (7)：
A isX2、X3It is expressed as oxygen atom, sulphur atom, selenium atom, C1-10Straight chain or One of tertiary amine groups that the alkylidene of alkyl group replacement, the alkylidene of aryl replacement, alkyl or aryl replace；A passes through CL1- CL2Key, CL2-CL3Key, CL3-CL4Key, CL4-CL5Key, CL‘1-CL’2Key, CL‘2-CL’3Key, CL‘3-CL’4Key or CL‘4-CL’5Bonded On formula (2) or formula (4)；
Ar2、Ar3Independently be expressed as phenyl, C1-10Straight or branched alkyl replace phenyl, dibiphenylyl, three One of phenyl or naphthyl；
R3、R4Independently be expressed as hydrogen atom, carbon atom is the alkyl of 1-10, replacement or unsubstituted carbon atom The carbon atom that aryl for 1-50, aryl or alkyl replace is amido, replacement or the unsubstituted carbon atom of 1-50 is 1-50 Heteroaryl.
Preferably, described R3、R4Carbon atom of choosing independently is the alkyl of 1-10, phenyl, C1-10Straight or branched alkane Knot shown in phenyl, dibiphenylyl, terphenyl, naphthyl, formula (8), formula (9), formula (10) or the formula (11) that base replaces Structure；
Wherein, Ar4、Ar5、Ar6Expression phenyl independently, C1-10The phenyl of straight or branched alkyl replacement, biphenyl Base, terphenyl, naphthyl, C1-10The benzofuranyl of straight or branched alkyl replacement, C1-10The benzene that straight or branched alkyl replaces Bithiophene base, C1-10The fluorenyl of straight or branched alkyl replacement, C1-10One of carbazyl that straight or branched alkyl replaces；
R5、R6Choose hydrogen, the carbon atom alkyl for 1-10 or carbon atom independently are the aromatic radical of 4-20；
X4It is expressed as oxygen atom, sulphur atom, selenium atom, C1-10The alkylidene that straight or branched alkyl replaces, aryl replace One of tertiary amine groups that alkylidene, alkyl or aryl replace.
Preferably, Ar is expressed asWhen, the general structure of described compound is expressed as：
In any one.
Preferably, when Ar is expressed as-R, the general structure of described compound is expressed as：
In any one.
Preferably, in described formula (1), R is：
In any one.
Preferably, the concrete structure of the described compound with anthrone as core is：
In any one.
The applicant additionally provides a kind of luminescent device comprising described compound, and described compound is as luminescent layer material Material, for making organic electroluminescence device.
Preferably, described compound is as luminescent layer material of main part, for making organic electroluminescence device.
The applicant additionally provides a kind of method preparing described compound, the reaction equation occurring in preparation process It is：
Formula 1 course of reaction is as follows：Weigh the bromo compound that anthrone is core and R-H, dissolved with toluene；Add Pd2 (dba)3, tri-butyl phosphine, sodium tert-butoxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reaction temperature 95～ 110 DEG C, react 10～24 hours, cooling, filtering reacting solution, filtrate revolving, cross silicagel column, obtain target product；
Described anthrone is the bromide of core is 1 with the mol ratio of R-H:1.0～4.0；Pd2(dba)3It is core with anthrone Bromide mol ratio be 0.006～0.02:1, the mol ratio of the bromide that tri-butyl phosphine is core with anthrone is 0.006 ～0.02:1, the mol ratio of the bromide that sodium tert-butoxide is core with anthrone is 1.0～4.0:1；
Formula 2 course of reaction is as follows：Weigh the bromo compound that anthrone is core and Ar-B (OH)2, dissolved with toluene；Again plus Enter Pd (PPh3)4, sodium carbonate；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in 95～110 DEG C of reaction temperature, reaction 10～24 hours, cooling, filtering reacting solution, filtrate revolving, cross silicagel column, obtain target product；
Described anthrone is bromide and the Ar-B (OH) of core2Mol ratio be 1:1.0～4.0；Pd(PPh3)4With anthrone Mol ratio for the bromide of core is 0.006～0.02:1, the mol ratio of the bromide that sodium carbonate is core with anthrone is 1.0 ～4.0:1.
Beneficial the having technical effect that of the present invention：
The compounds of this invention with anthrone as parent nucleus, the crystallinity of saboteur, it is to avoid intermolecular aggregation, have Good heat stability；Described compound structure intramolecular comprise electron donor (donor, D) and electron acceptor (acceptor, A combination) can increase Orbital Overlap, improve luminous efficiency, be simultaneously connected with aromatic heterocycle group to obtain HOMO, LUMO space Detached charge transfer state material, realizes the energy level difference of little S1 state and T1 state, thus realizing inverse system under the conditions of thermostimulation Between alter more, be suitable as emitting layer material material of main part use.
Compound of the present invention can be applied to OLED luminescent device as luminescent layer material of main part and make, and obtain good Device performance, the current efficiency of device, power efficiency and external quantum efficiency are all greatly improved；Simultaneously for the device longevity Life lifting is clearly.Compound-material of the present invention has good application effect in OLED luminescent device, has good Good industrialization prospect.
Brief description
The device architecture schematic diagram that Fig. 1 applies for the compounds of this invention；
Wherein, 1 is transparent substrate layer, and 2 is ito anode layer, and 3 is hole injection layer, and 4 is hole transmission layer, and 5 is luminous Layer, 6 is electron transfer layer, and 7 is electron injecting layer, and 8 is negative electrode layer.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
The synthesis of embodiment 1 compound C03
The four-hole bottle of 250ml, under the atmosphere being passed through nitrogen, adds 0.01mol 2- bromo- 10,10- dimethyl -10H- anthracene Ketone, 0.015mol compound A1,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphine, 150ml toluene, is heated to reflux 24 hours, sample point plate, and reaction is complete, natural cooling, filters, filtrate revolving, crosses silicagel column, obtains To target product, purity 99.40%, yield 36.90%.
HPLC-MS：Material molecule amount is 686.29, surveys molecular weight 686.31.
The synthesis of embodiment 2 compound C11
The four-hole bottle of 250ml, under the atmosphere being passed through nitrogen, adds 0.01mol 3- (3- bromophenyl) -10,10- hexichol Base -10H- anthrone, 0.015molA2,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert Phosphine, 150ml toluene, it is heated to reflux 24 hours, sample point plate, reaction is complete, natural cooling, filters, filtrate revolving, cross silica gel Post, obtains target product, purity 97.6%, yield 45.8%.
HPLC-MS：Material molecule amount is 912.41, surveys molecular weight 912.59.
The synthesis of embodiment 3 compound C24
The four-hole bottle of 500ml, under the atmosphere being passed through nitrogen, adds 0.01mo 3- bromo- 10,10- diphenyl -10H- anthracene Ketone, 0.015molA3, dissolves (180ml toluene, 90ml ethanol) with mixed solvent, is subsequently adding 0.03mol Na2CO3Aqueous solution (2M), it is subsequently adding 0.0001mol Pd (PPh3)4, it is heated to reflux 10-24 hour, sample point plate, reaction is completely.Natural cooling, Filter, filtrate revolving, cross silicagel column, obtain target product, HPLC purity 99.50%, yield 56.5%.
HPLC-MS：Material molecule amount is 683.32, surveys molecular weight 683.42.
The synthesis of embodiment 4 compound C31
The four-hole bottle of 500ml, under the atmosphere being passed through nitrogen, adds 0.01mo 3- bromo- 10,10- dimethyl -10H- anthracene Ketone, 0.015molA4, dissolves (180ml toluene, 90ml ethanol) with mixed solvent, is subsequently adding 0.03molNa2CO3Aqueous solution (2M), it is subsequently adding 0.0001mol Pd (PPh3)4, it is heated to reflux 10-24 hour, sample point plate, reaction is completely.Natural cooling, Filter, filtrate revolving, cross silicagel column, obtain target product, HPLC purity 99.5%, yield 38.60%.
HPLC-MS：Material molecule amount is 712.35, surveys molecular weight 712.4.
The synthesis of embodiment 5 compound C36
The four-hole bottle of 250ml, under the atmosphere being passed through nitrogen, adds 0.01mol 3- (4- bromophenyl) -10,10- diformazan Base -10H- anthrone, 0.015molA5,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert Phosphine, 150ml toluene, it is heated to reflux 24 hours, sample point plate, reaction is complete, natural cooling, filters, filtrate revolving, cross silica gel Post, obtains target product, purity 97.2%, yield 45.6%.
HPLC-MS：Material molecule amount is 781.33, surveys molecular weight 781.28.
The synthesis of embodiment 6 compound C48
The four-hole bottle of 500ml, under the atmosphere being passed through nitrogen, adds 0.01mo 2- bromo- 10,10- diphenyl -10H- anthracene Ketone, 0.015molA3, dissolves (180ml toluene, 90ml ethanol) with mixed solvent, is subsequently adding 0.03molNa2CO3Aqueous solution (2M), it is subsequently adding 0.0001mol Pd (PPh3)4, it is heated to reflux 10-24 hour, sample point plate, reaction is completely.Natural cooling, Filter, filtrate revolving, cross silicagel column, obtain target product, HPLC purity 99.2%, yield 56.3%.
HPLC-MS：Material molecule amount is 887.39, surveys molecular weight 887.42.
The synthesis of embodiment 7 compound C50
The four-hole bottle of 250ml, under the atmosphere being passed through nitrogen, adds 0.01mol 3- (4- bromophenyl) -10,10- diformazan Base -10H- anthrone, 0.015molA7,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert Phosphine, 150ml toluene, it is heated to reflux 24 hours, sample point plate, reaction is complete, natural cooling, filters, filtrate revolving, cross silica gel Post, obtains target product, purity 97.1%, yield 45.8%.
HPLC-MS：Material molecule amount is 963.42, surveys molecular weight 963.38.
The synthesis of embodiment 8 compound C60
The four-hole bottle of 250ml, under the atmosphere being passed through nitrogen, adds 0.01mol 3- bromo- 10,10- dimethyl -10H- anthracene Ketone, 0.015molA8,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphine, 150ml Toluene, is heated to reflux 24 hours, sample point plate, and reaction is complete, natural cooling, filters, filtrate revolving, crosses silicagel column, obtains mesh Mark product, purity 96.8%, yield 45.4%.
HPLC-MS：Material molecule amount is 768.41, surveys molecular weight 768.35.
The synthesis of embodiment 9 compound C64
The four-hole bottle of 250ml, under the atmosphere being passed through nitrogen, adds 0.01mol 3- (4- bromophenyl) -10,10- diformazan Base -10H- anthrone, 0.015molA9,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert Phosphine, 150ml toluene, it is heated to reflux 24 hours, sample point plate, reaction is complete, natural cooling, filters, filtrate revolving, cross silica gel Post, obtains target product, purity 97.5%, yield 45.6%.
HPLC-MS：Material molecule amount is 872.38, surveys molecular weight 872.42.
The synthesis of embodiment 10 compound C71
The four-hole bottle of 250ml, under the atmosphere being passed through nitrogen, adds 0.01mol 3- (4- bromophenyl) -10,10- diformazan Base -10H- anthrone, 0.015molA10,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert Phosphine, 150ml toluene, it is heated to reflux 24 hours, sample point plate, reaction is complete, natural cooling, filters, filtrate revolving, cross silica gel Post, obtains target product, purity 97.1%, yield 46.6%.
HPLC-MS：Material molecule amount is 835.36, surveys molecular weight 835.42.
The synthesis of embodiment 11 compound C79
The four-hole bottle of 250ml, under the atmosphere being passed through nitrogen, adds 0.01mol 3- (3- bromophenyl) -10,10- hexichol Base -10H- anthrone, 0.015molA11,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert Phosphine, 150ml toluene, it is heated to reflux 24 hours, sample point plate, reaction is complete, natural cooling, filters, filtrate revolving, cross silica gel Post, obtains target product, purity 97.2%, yield 44.3%.
HPLC-MS：Material molecule amount is 844.31, surveys molecular weight 844.36.
The synthesis of embodiment 12 compound C109
The four-hole bottle of 500ml, under the atmosphere being passed through nitrogen, adds 0.01mo 3- bromo- 10,10- diphenyl -10H- anthracene Ketone, 0.015molA12, dissolves (180ml toluene, 90ml ethanol) with mixed solvent, is subsequently adding 0.03molNa2CO3Aqueous solution (2M), it is subsequently adding 0.0001mol Pd (PPh3)4, it is heated to reflux 10-24 hour, sample point plate, reaction is completely.Natural cooling, Filter, filtrate revolving, cross silicagel column, obtain target product, HPLC purity 96.50%, yield 53.5%.
HPLC-MS：Material molecule amount is 768.28, surveys molecular weight 768.34.
The synthesis of embodiment 13 compound C121
The four-hole bottle of 500ml, under the atmosphere being passed through nitrogen, adds 0.01mo 3- bromo- 10,10- dimethyl -10H- anthracene Ketone, 0.015molA13, dissolves (180ml toluene, 90ml ethanol) with mixed solvent, is subsequently adding 0.03molNa2CO3Aqueous solution (2M), it is subsequently adding 0.0001mol Pd (PPh3)4, it is heated to reflux 10-24 hour, sample point plate, reaction is completely.Natural cooling, Filter, filtrate revolving, cross silicagel column, obtain target product, HPLC purity 94.50%, yield 52.5%.
HPLC-MS：Material molecule amount is 871.38, surveys molecular weight 871.42.
The synthesis of embodiment 14 compound C123
The four-hole bottle of 500ml, under the atmosphere being passed through nitrogen, adds 0.01mo 2- bromo- 10,10- dimethyl -10H- anthracene Ketone, 0.015molA14, dissolves (180ml toluene, 90ml ethanol) with mixed solvent, is subsequently adding 0.03molNa2CO3Aqueous solution (2M), it is subsequently adding 0.0001mol Pd (PPh3)4, it is heated to reflux 10-24 hour, sample point plate, reaction is completely.Natural cooling, Filter, filtrate revolving, cross silicagel column, obtain target product, HPLC purity 91.50%, yield 53.5%.
HPLC-MS：Material molecule amount is 645.23, surveys molecular weight 645.35.
The synthesis of embodiment 15 compound C132
The four-hole bottle of 500ml, under the atmosphere being passed through nitrogen, adds 0.01mo 2- (3,5- dibromo phenyl) -10,10- bis- Methyl isophthalic acid 0H- anthrone, 0.015molA15, dissolves (180ml toluene, 90ml ethanol) with mixed solvent, is subsequently adding 0.03molNa2CO3Aqueous solution (2M), is subsequently adding 0.0001mol Pd (PPh3)4, it is heated to reflux 10-24 hour, sample point Plate, reaction is completely.Natural cooling, filters, filtrate revolving, crosses silicagel column, obtains target product, HPLC purity 97.10%, yield 30.60%.
HPLC-MS：Material molecule amount is 814.27, surveys molecular weight 814.32.
The synthesis of embodiment 16 compound C133
The four-hole bottle of 250ml, under the atmosphere being passed through nitrogen, adds 0.01mol 3,6- (4- bromophenyl) -10,10- bis- Methyl isophthalic acid 0H- anthrone, 0.03molA16,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4The tertiary fourth of mol tri- Base phosphine, 150ml toluene, it is heated to reflux 24 hours, sample point plate, reaction is complete, natural cooling, filters, filtrate revolving, cross silica gel Post, obtains target product, purity 98.61%, yield 49.50%.
HPLC-MS：Material molecule amount is 1122.52, surveys molecular weight 1122.48.
The synthesis of embodiment 17 compound C136
The four-hole bottle of 250ml, under the atmosphere being passed through nitrogen, adds 0.01mol 2- (4- bromophenyl) -10,10- hexichol Base -10H- anthrone, 0.03molA17,0.03mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert Phosphine, 150ml toluene, it is heated to reflux 24 hours, sample point plate, reaction is complete, natural cooling, filters, filtrate revolving, cross silica gel Post, obtains target product, purity 98.61%, yield 49.50%.
HPLC-MS：Material molecule amount is 753.30, surveys molecular weight 753.34.
The compounds of this invention can use as emitting layer material, to the compounds of this invention C36 and current material CBP respectively Carry out hot property, the mensure of HOMO energy level, testing result is as shown in table 1.
Table 1
Compound Tg(℃) Td(℃) HOMO energy level (eV) Function
Compound C36 153 412 -5.70 Material of main part
Compound CBP 113 353 -5.90 Material of main part
Note：Vitrification point Tg is by differential scanning calorimetry (DSC, German Nai Chi company DSC204F1 differential scanning calorimetry Instrument) measure, 10 DEG C/min of heating rate；Thermal weight loss temperature Td is in nitrogen atmosphere weightless 1% temperature, public in Japanese Shimadzu It is measured on the TGA-50H thermogravimetric analyzer of department, nitrogen flow is 20mL/min；Highest occupied molecular orbital HOMO energy level and Minimum occupied molecular orbital lumo energy is by photoelectron emissions spectrometer (AC-2 type PESA) and ultraviolet spectrophotometer (UV) Measuring and calculation gained, tests as atmospheric environment.
From upper table data, the compounds of this invention has a higher heat stability, suitable HOMO energy level, is suitable as For emitting layer material；Meanwhile, the compounds of this invention contains electron donor (donor, D) and electron acceptor (acceptor, A), makes The OLED electronics of the compounds of this invention and hole must be applied to reach poised state so that device efficiency and life-span are carried Rise.
18-25 and comparative example 1-3 describes the compound conduct in the devices of present invention synthesis in detail by the following examples The application effect of luminescent layer material of main part.Embodiment 19-25 compared with embodiment 18, the complete phase of processing technology of described device With, and employed identical baseplate material and electrode material, the thickness of electrode material is also consistent, except that device In part, the material of main part of luminescent layer there occurs change.Embodiment 18-25 compared with comparative example 1-3, device described in comparative example 1-3 Emitting layer material uses existing conventional raw material, and the device luminescent layer material of main part of embodiment 18-25 uses this Bright compound.The structure composition of each embodiment obtained device is as shown in table 2.The performance test results of each device are shown in Table 3.
Embodiment 18
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4 (compound C24 and GD-19 is according to 100 for (TAPC, thickness 80nm)/luminescent layer 5：5 weight is than blending, thickness 30nm)/electronics Transport layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).Each compound point Subformula is as follows：
Concrete preparation process is as follows：
Transparent substrate layer 1 adopts transparent material, such as glass；Ito anode layer 2 (thickness is 150nm) is washed, that is, according to Secondary carry out neutralizing treatment, pure water, be dried after carry out again ultraviolet-ozone wash to remove the organic residue on transparent ITO surface Thing.
On the ito anode layer 2 having carried out after above-mentioned washing, using vacuum deposition apparatus, being deposited with thickness is 10nm's Molybdenum trioxide MoO3Use as hole injection layer 3.And then the TAPC of evaporation 80nm thickness is as hole transmission layer 4.
After above-mentioned hole mobile material evaporation terminates, make the luminescent layer 5 of OLED luminescent device, its structure includes OLED and sends out As material of main part, as dopant material, dopant material doping ratio is 5% to GD-19 to the used material compound C02 of photosphere 5 Weight ratio, luminescent layer thickness is 30nm.
After above-mentioned luminescent layer 5, continuation vacuum evaporation electron transport layer materials are TPBI, the vacuum evaporation coating of this material Thick is 40nm, and this layer is electron transfer layer 6.
On electron transfer layer 6, by vacuum deposition apparatus, make lithium fluoride (LiF) layer that thickness is 1nm, this layer is Electron injecting layer 7.
On electron injecting layer 7, by vacuum deposition apparatus, make aluminum (Al) layer that thickness is 80nm, this layer is negative electrode Reflection electrode layer 8 uses.
After OLED luminescent device accomplished as described above, with known drive circuit, anode and negative electrode are coupled together, survey The I-E characteristic of the luminous efficiency of metering device, luminescent spectrum and device.
Embodiment 19
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4 (compound C36 and GD-19 is according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:5 weight is than blending, thickness 30nm)/electronics Transport layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Embodiment 20
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4 (compound C24 and Ir (PPy) 3 is according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:10 weight is than blending, thickness 30nm)/ Electron transfer layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Embodiment 21
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4 (compound C31 and Ir (PPy) 3 is according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:10 weight is than blending, thickness 30nm)/ Electron transfer layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Embodiment 22
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4 (compound 36 and GD-PACTZ are according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:5 weight is than blending, thickness 30nm)/electricity Sub- transport layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Embodiment 23
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4 (compound C71 and GD-PACTZ is according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:5 weight is than blending, thickness 30nm)/electricity Sub- transport layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Embodiment 24
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4 (compound C123, GH-204 and Ir (PPy) 3 is according to 70 for (TAPC, thickness 80nm)/luminescent layer 5:30:10 weight than blending, Thickness 30nm)/electron transfer layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Embodiment 25
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4 (compound C136, GH-204 and GD-PACTZ are according to 70 for (TAPC, thickness 80nm)/luminescent layer 5:30:5 weight is than blending, thick Degree 30nm)/electron transfer layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Comparative example 1
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4 (CBP and GD-19 is according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:5 weight is than blending, thickness 30nm)/electron transfer layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Comparative example 2
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4 (CBP and Ir (PPy) 3 is according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:10 weight is than blending, thickness 30nm)/electronics biography Defeated layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
Comparative example 3
Transparent substrate layer 1/ITO anode layer 2/ hole injection layer 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4 (CBP and GD-PACTZ is according to 100 for (TAPC, thickness 80nm)/luminescent layer 5:5 weight is than blending, thickness 30nm)/electric transmission Layer 6 (TPBI, thickness 40nm)/electron injecting layer 7 (LiF, thickness 1nm)/negative electrode layer 8 (Al).
The test result of made OLED luminescent device is shown in Table 3.
Table 2
Table 3
Compound of the present invention can be applied as luminescent layer material of main part and light with OLED from the results shown in Table 3 Element manufacturing, and compared with comparative example 1-3, either efficiency or life-span all ratio known OLED material larger changes of acquisition, The life-span that drives of particularly device obtains larger lifting.
From the point of view of data above application, the compounds of this invention has well as emitting layer material in OLED luminescent device Application effect, there is good industrialization prospect.
Although the present invention has been disclosed by embodiment and preferred implementation it should be appreciated that the invention is not restricted to institute's public affairs 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 The scope of attached claim should arrangement to cover all such modifications and be similar to consistent with explanation the widest.

Claims (9)

1. a kind of compound with anthrone as core is it is characterised in that the structure such as formula (1) of described compound is shown：
In formula (1), D1、D2Selection C independently1-10One of straight or branched alkyl or phenyl, D1、D2Permissible Identical or different；Ar representsOr；Wherein, Ar1Represent phenyl, dibiphenylyl, terphenyl, naphthyl, Anthryl or phenanthryl；M, n selection 1 or 2 independently；
DescribedRepresent (Ar)mIt is connected on any carbon atom on the phenyl ring of formula (1) both sides；
R adopts formula (2), formula (3), formula (4) or formula (5) to represent：
Wherein,
X1, Y be oxygen atom, sulphur atom, selenium atom, C1-10The alkylene that the alkylidene of straight or branched alkyl replacement, aryl replace One of tertiary amine groups that base, alkyl or aryl replace；
R1Choose structure shown in formula (6), R2Choose structure shown in formula (7)：
A isX2、X3It is expressed as oxygen atom, sulphur atom, selenium atom, C1-10Straight or branched alkane One of tertiary amine groups that the alkylidene of base replacement, the alkylidene of aryl replacement, alkyl or aryl replace；A passes through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL4-CL5Key, CL‘1-CL’2Key, CL‘2-CL’3Key, CL‘3-CL’4Key or CL‘4-CL’5Bonded in formula (2) or on formula (4)；
Ar2、Ar3Independently be expressed as phenyl, C1-10The phenyl of straight or branched alkyl replacement, dibiphenylyl, terphenyl One of base or naphthyl；
R3、R4Be expressed as hydrogen atom, the carbon atom alkyl for 1-10, replacement or unsubstituted carbon atom independently are 1- The carbon atom that 50 aryl, aryl or alkyl replace is amido, replacement or the unsubstituted carbon atom of 1-50 is the miscellaneous of 1-50 Aryl.
2. compound according to claim 1 is it is characterised in that described R3、R4Selection carbon atom independently is 1-10 Alkyl, phenyl, C1-10The phenyl of straight or branched alkyl replacement, dibiphenylyl, terphenyl, naphthyl, formula (8), formula (9), formula (10) or structure shown in formula (11)；
Wherein, Ar4、Ar5、Ar6Expression phenyl independently, C1-10Straight or branched alkyl replace phenyl, dibiphenylyl, three Xenyl, naphthyl, C1-10The benzofuranyl of straight or branched alkyl replacement, C1-10The benzo thiophene that straight or branched alkyl replaces Fen base, C1-10The fluorenyl of straight or branched alkyl replacement, C1-10One of carbazyl that straight or branched alkyl replaces；
R5、R6Choose hydrogen, the carbon atom alkyl for 1-10 or carbon atom independently are the aromatic radical of 4-20；
X4It is expressed as oxygen atom, sulphur atom, selenium atom, C1-10The alkylene that the alkylidene of straight or branched alkyl replacement, aryl replace One of tertiary amine groups that base, alkyl or aryl replace.
3. compound according to claim 1 is it is characterised in that Ar is expressed asWhen, the structure of described compound Formula is expressed as：
In any one.
4. compound according to claim 1 is it is characterised in that when Ar is expressed as-R, the general structure table of described compound It is shown as：
In any one.
5. compound according to claim 1 it is characterised in that in described formula (1) R be：
In any one.
6. compound according to claim 1 is it is characterised in that the concrete structure of the described compound with anthrone as core For：
In any one.
7. a kind of luminescent device comprising compound described in any one of claim 1～6 is it is characterised in that described compound conduct Emitting layer material, for making organic electroluminescence device.
8. luminescent device according to claim 7 is it is characterised in that described compound, as luminescent layer material of main part, is used for Make organic electroluminescence device.
9. a kind of method preparing compound described in any one of claim 1～6 is it is characterised in that occur in preparation process is anti- The equation is answered to be：
Formula 1 course of reaction is as follows：Weigh the bromo compound that anthrone is core and R-H, dissolved with toluene；Add Pd2 (dba)3, tri-butyl phosphine, sodium tert-butoxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in reaction temperature 95～ 110 DEG C, react 10～24 hours, cooling, filtering reacting solution, filtrate revolving, cross silicagel column, obtain target product；
Described anthrone is the bromide of core is 1 with the mol ratio of R-H:1.0～4.0；Pd2(dba)3With anthrone for core bromine The mol ratio of compound is 0.006～0.02:1, tri-butyl phosphine and anthrone be the bromide of core mol ratio be 0.006～ 0.02:1, the mol ratio of the bromide that sodium tert-butoxide is core with anthrone is 1.0～4.0:1；
Formula 2 course of reaction is as follows：Weigh the bromo compound that anthrone is core and Ar-B (OH)2, dissolved with toluene；Add Pd (PPh3)4, sodium carbonate；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in 95～110 DEG C of reaction temperature, reaction 10～ 24 hours, cooling, filtering reacting solution, filtrate revolving, cross silicagel column, obtain target product；
Described anthrone is bromide and the Ar-B (OH) of core2Mol ratio be 1:1.0～4.0；Pd(PPh3)4It is core with anthrone The mol ratio of the bromide of the heart is 0.006～0.02:1, sodium carbonate and anthrone be the bromide of core mol ratio be 1.0～ 4.0:1.
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