It is a kind of using cyano benzene as the compound of core and its in organic electroluminescence device
Using
Technical field
The present invention relates to technical field of semiconductors, as the compound of core and its are having more particularly, to a kind of using cyano benzene
The application of organic electroluminescence devices.
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 it is clipped in different electricity
Organic functional material between the film layer of pole, various different function materials are overlapped mutually depending on the application collectively constitutes OLED hair together
Optical device.As current device, when the two end electrodes application voltage to OLED luminescent device, and pass through electric field action organic layer function
Positive and negative charge in energy 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 poor (the △ E of small singlet-tripletST), 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→S1State 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.Current OLED is shown to the actual demand of Lighting Industry
For, the development of OLED material is also far from enough at present, lags behind the requirement of panel manufacturing enterprise, more as material enterprise development
High performance organic functional material is particularly important.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provide it is a kind of using cyano benzene as the compound of core and
Its application in OLED device.The compounds of this invention is based on TADF mechanism using cyano benzene as core, answers as emitting layer material
For Organic Light Emitting Diode, the device that the present invention makes has good photoelectric properties, can satisfy panel manufacturing enterprise
It is required that.
Technical scheme is as follows: a kind of using cyano benzene as the compound of core, the structure of the compound is such as logical
Shown in formula (1):
In general formula (1), X1、X2And X3Independently be expressed as cyano or hydrogen atom;X1、X2And X3It is not former for hydrogen simultaneously
Son;
In general formula (1), R1、R2Independently be expressed as hydrogen atom, substituted or unsubstituted C6-60Aryl contains one
Or multiple heteroatomic substituted or unsubstituted 5-60 unit's heteroaryls;The hetero atom is nitrogen, oxygen or sulphur;R1With R2It is not simultaneously
Hydrogen atom;
In general formula (1), Ar is expressed as singly-bound, substituted or unsubstituted C6-60Arlydene contains one or more hetero atoms
Substituted or unsubstituted 5~60 yuan of heteroarylidenes;The hetero atom is nitrogen, oxygen or sulphur;
In general formula (1), R3It is expressed as structure shown in general formula (2) or general formula (3):
In general formula (1), R4It is expressed as structure shown in general formula (4), general formula (5) or general formula (6):
In general formula (3), general formula (6), R5、R6、R7、R8Independently be expressed as substituted or unsubstituted C6-60Aryl contains
There are one or more heteroatomic substituted or unsubstituted 5~60 unit's heteroaryls;The hetero atom is nitrogen, oxygen or sulphur;
In general formula (4), X4It is expressed as oxygen, sulphur, C1-10The alkylene of alkylidene, aryl substitution that linear or branched alkyl group replaces
One of the imido grpup that base, alkyl-substituted imido grpup or aryl replace;
General formula (4), general formula (5) pass through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key is connected with general formula (1) and ring.
On the basis of above scheme, the present invention can also do following improvement.
Preferably, a kind of using cyano benzene as the compound of core, the structure of the compound such as general formula (7), general formula (8),
Shown in general formula (9), general formula (10) or general formula (11):
Preferably, a kind of using cyano benzene as the compound of core, R1、R2Independently be expressed as hydrogen atom, phenyl, connection
Phenyl, naphthalene or anthryl;Ar is expressed as one kind of singly-bound, phenylene, biphenylene, naphthylene or anthrylene;R5、R6、R7、R8
Independently be expressed as phenyl, naphthalene, dibiphenylyl, terphenyl, dibenzofurans, 9,9- dimethyl fluorene or N- phenyl click
One of azoles.
Preferably, a kind of using cyano benzene as the compound of core, in general formula (1)It indicates are as follows:
In it is any
It is a kind of.
Preferably, a kind of using cyano benzene as the compound of core, it is describedIt indicates are as follows:
In any one.
Preferably, a kind of using cyano benzene as the compound of core, the concrete structure formula of the compound are as follows:
In any one.
The present invention also provides a kind of using cyano benzene as the method for the compound of core, the reactional equation occurred in preparation process
Formula is:
When Ar indicates singly-bound:
Specific preparation step are as follows:
Raw material bromo-derivative E1 and intermediate M1 are dissolved in dry toluene, Pd is added after deoxygenation2(dba)3And tri-tert
Phosphorus, under an inert atmosphere 95~110 DEG C of 10~24 hours of reaction constantly monitor reaction process with TLC in reaction process, to original
After expecting fully reacting, filtrate is rotated and removes dry toluene by cooling, filtering, and crude product crosses silicagel column, obtains target compound;
The dosage of the dry toluene is that every gram of intermediate M1 uses 30~50mL toluene, and bromo-derivative E1 and the molar ratio of intermediate M1 are
1:1.0~1.5, Pd2(dba)3Molar ratio with bromo-derivative E1 is 0.006~0.02:1, and tri-tert-butylphosphine rubs with bromo-derivative E1's
, than being 0.006~0.02:1, the molar ratio of sodium tert-butoxide and bromo-derivative E1 are 2.0~3.0:1 for you;
When Ar does not indicate singly-bound
Intermediate M2 and raw material E2 are dissolved in the mixed solution of toluene and ethyl alcohol, Pd (PPh is added after deoxygenation3)4With
K2CO3, 95~110 DEG C of 10~24 hours of reaction under an inert atmosphere constantly monitor reaction process with TLC in reaction process, to
After raw material fully reacting, filtrate is rotated and removes solvent by cooling, filtering, and crude product crosses silicagel column, obtains target compound;Institute
The dosage of the toluene and ethyl alcohol stated is that every gram of intermediate M2 uses 30~50mL toluene and 5~10mL ethyl alcohol, raw material E2 and centre
The molar ratio of body M2 is (1~1.5): 1, Pd (PPh3)4Molar ratio with intermediate M2 is (0.006~0.02): 1, K2CO3With
The molar ratio of intermediate M2 is (1.5~2): 1.
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device includes at least one layer of function
Layer is containing described using cyano benzene as the compound of core.
Preferably, a kind of organic electroluminescence device, including luminescent layer, the luminescent layer contains described is with cyano benzene
The compound of core.
The present invention also provides a kind of illumination or display elements, including the organic electroluminescence device.
The present invention is beneficial to be had the technical effect that
For the compounds of this invention using cyano benzene as parent nucleus, cyano-phenyl group is in approximately the same plane, have stronger rigidity and
Better film forming;Cyano-phenyl group is strong electron-withdrawing group group, can be formed with carbazole and ring and two fragrant imines groups stronger
Electric charge transfer effect, and the energy level difference with lesser S1 state and T1 state, to be altered between realizing inverse system under the conditions of thermostimulation
More, under conditions of energy level meets while there is bipolarity and TADF effect;Simultaneously because the chemical stability and heat of cyano are steady
Qualitative, cyano benzene has preferable prospects for commercial application, is suitable as the use of luminescent layer material of main part.Further, according to material
Expect the difference of MOLECULE DESIGN, the dopant material that such compound can also be used as emitting layer material uses.
The compounds of this invention as OLED luminescent device emitting layer material in use, device current efficiency, power effect
Rate and external quantum efficiency are greatly improved;Meanwhile device lifetime is promoted clearly.Compound material of the present invention
Material has good application effect in OLED luminescent device, has good industrialization prospect.
Detailed description of the invention
Fig. 1 is the device architecture schematic diagram of the compounds of this invention application;
Wherein, 1 is transparent substrate layer, and 2 be ito anode layer, and 3 be hole injection layer, and 4 be hole transmission layer, and 5 be luminous
Layer, 6 be electron transfer layer, and 7 be electron injecting layer, and 8 be cathode reflection electrode layer;
Fig. 2 is current efficiency variation with temperature curve.
Specific embodiment
Embodiment 1:
It provides in general formula (1) firstSynthetic route are as follows:
It weighs raw material I to be dissolved in acetic acid, is cooled to 0 DEG C with ice salt bath;Bromine is weighed to be dissolved in glacial acetic acid, be slowly added dropwise to
In acetic acid solution containing nitro compound raw material I, reaction is stirred at room temperature 6~12 hours, samples contact plate, display is surplus without raw material I
Remaining, reaction terminates, and sodium hydrate aqueous solution, which is added dropwise, makes the aobvious neutrality of reaction solution, is extracted with dichloromethane, organic phase is taken to filter, filtrate
Vacuum rotary steam crosses silicagel column, obtains intermediate S1 to no fraction;In above-mentioned reaction, the molar ratio of raw material I and bromine be 1:1~
3;Every gram of raw material I uses 30~50mL acetic acid;
Weigh raw material II and intermediate S1, dissolved with toluene, under an inert atmosphere, be added potassium carbonate, tetra-triphenylphosphine palladium,
The mixed solution of second alcohol and water, stirring are warming up to 110~120 DEG C, react 10~24 hours, sample contact plate, show without intermediate
S1 is remaining, and reaction terminates, is cooled to room temperature, and filters, filtrate layered, takes organic phase vacuum rotary steam to no fraction, crosses silicagel column, obtain
To intermediate S2;In above-mentioned reaction, the molar ratio of intermediate S1 and raw material II is 1:1~2;Mole of intermediate S1 and potassium carbonate
Than for 1:1~3;The molar ratio of intermediate S1 and tetra-triphenylphosphine palladium is 1:0.01~0.05;
Under an inert atmosphere, intermediate S2 is dissolved in o-dichlorohenzene, adds triphenylphosphine, stirred at 170~190 DEG C
It mixes reaction 12~16 hours, samples contact plate, display is remaining without intermediate S2, and reaction terminates, is cooled to room temperature, and filters, and filtrate subtracts
Pressure revolving crosses silicagel column, obtains intermediate M1 to o-dichlorohenzene;In above-mentioned reaction, intermediate S2 is with triphenylphosphine molar ratio
1:1~2;Every gram of intermediate S2 uses 30~50mL o-dichlorohenzene;
Under nitrogen protection, intermediate M1, raw material III, sodium tert-butoxide, Pd are successively weighed2(dba)3, tri-tert-butylphosphine, use
Toluene is stirred, and is heated to 110~120 DEG C, back flow reaction 12~24 hours, is sampled contact plate, and display is remaining without intermediate M1,
Fully reacting;Cooled to room temperature, filtering, filtrate carry out vacuum rotary steam to no toluene, cross neutral silica gel column, obtain intermediate
M2.In above-mentioned reaction, intermediate M1 and III molar ratio of raw material are 1:1~2;The molar ratio of intermediate M1 and sodium tert-butoxide is 1:1
~3;Intermediate M1 and Pd2(dba)3Molar ratio be 1:0.01~0.05;The molar ratio of intermediate M1 and tri-tert-butylphosphine is 1:
0.01~0.05;Every gram of intermediate M1 uses 30~50mL toluene.
By taking intermediate M2-3 as an example:
In the there-necked flask of 250ml, raw material I-1,100ml acetic acid of 0.04mol is added, stirring and dissolving is dropped with ice salt bath
Temperature is to 0 DEG C;Weigh 0.05mol Br2It is dissolved in 50ml acetic acid, the acetic acid solution of bromine is slowly added dropwise into above-mentioned reaction system, is dripped
It after adding, is warmed to room temperature, is stirred to react 12 hours;Contact plate is sampled, display is remaining without raw material I-1, fully reacting;Add NaOH water
Solution neutralization reaction liquid is extracted with dichloromethane to neutrality, is layered, takes organic phase to filter, filtrate decompression is rotated to no fraction, mistake
Neutral silica gel column obtains intermediate S1-1;Elemental analysis structure C10H6BrNO2: theoretical value C, 47.65;H,2.40;Br,
31.70;N,5.56;Test value: C, 47.65;H,2.40;Br,31.70;N,5.55;ESI-MS (m/z) (M+): theoretical value is
250.96 measured value 251.66.
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.05mol intermediate S1-1,0.06mol raw material II -2,
100ml toluene, is stirred, and adds 0.0025mol Pd (PPh3)4, 0.075mol potassium carbonate, 50ml water and ethyl alcohol 1:1
Mixed liquor, stirring are warming up to 120 DEG C, back flow reaction 24 hours, sample contact plate, display is remaining without intermediate S1-1, fully reacting;
Cooled to room temperature, filtering, filtrate layered take organic phase vacuum rotary steam to no fraction, cross neutral silica gel column, obtain intermediate
S2-2;Elemental analysis structure C22H15NO2: theoretical value C, 81.21;H,4.65;N,4.30;Test value: C, 81.21;H,4.65;N,
4.31;ESI-MS (m/z) (M+): theoretical value 325.11, measured value 325.44.
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.04mol intermediate S2-2,0.05mol triphenylphosphine,
100ml o-dichlorohenzene, is stirred, and is heated to 180 DEG C, reacts 12 hours, samples contact plate, and display is remaining without intermediate S2-2,
Fully reacting;Cooled to room temperature, filtering, filtrate decompression rotate to no fraction, cross neutral silica gel column, obtain intermediate M1-
2;Elemental analysis structure C22H15N: theoretical value C, 90.07;H,5.15;N,4.77;Test value: C, 90.08;H,5.15;N,
4.76;ESI-MS (m/z) (M+): theoretical value 293.12, measured value 293.22.
In the there-necked flask of 250ml, lead under nitrogen protection, 0.03mol intermediate M1-2,0.036mol Isosorbide-5-Nitrae-two is added
Bromobenzene, 150ml toluene, are stirred, and add 0.09mol sodium tert-butoxide, 0.002molPd2(dba)3, the tertiary fourth of 0.002mol tri-
Base phosphine is heated with stirring to 115 DEG C, back flow reaction 24 hours, samples contact plate, display is remaining without intermediate M1-2, fully reacting;From
It is so cooled to room temperature, filters, filtrate decompression is rotated to no fraction, is crossed neutral silica gel column, is obtained intermediate M2-3;Elemental analysis knot
Structure C28H18BrN: theoretical value C, 75.01;H,4.05;Br,17.82;N,3.12;Test value: C, 75.02;H,4.05;Br,
17.82;N,3.11;ESI-MS (m/z) (M+): theoretical value 447.06, measured value 447.51.
Intermediate M1 and M2 are prepared by the synthetic schemes of intermediate M2-3;Specific structure employed in preparation process is such as
Shown in table 1:
Table 1
Embodiment 2: the synthesis of compound 7:
0.01mol raw material E1-1 and 0.012mol intermediate M1-1 are dissolved in 150mL dry toluene, are added after deoxygenation
0.0005mol Pd2(dba)3, 0.015mol tri-tert phosphorus and 0.02mol sodium tert-butoxide, 110 DEG C of reactions under an inert atmosphere
24 hours constantly monitor reaction process with TLC in reaction process, and after raw material fully reacting, filtrate is revolved in cooling, filtering
Solvent is evaporated off, crude product crosses silicagel column, obtains target product;Elemental analysis structure (molecular formula C47H31N3): theoretical value C,
88.51;H,4.90;N,6.59;Test value: C, 88.52;H,4.90;N,6.58;ESI-MS (m/z) (M+): theoretical value is
637.25 measured value 637.76.
Embodiment 3: the synthesis of compound 17:
0.01mol intermediate M2-3 and 0.012mol raw material E2-1 is dissolved in the 150mL (V of toluene and ethyl alcoholToluene: VEthyl alcohol
=5:1) in mixed solution, 0.0002mol Pd (PPh is added after deoxygenation3)4With 0.02mol K2CO3, under an inert atmosphere 110
DEG C 24 hours of reaction, reaction process constantly are monitored with TLC in reaction process, after raw material fully reacting, cooling, filtering will
Filtrate revolving removes solvent, and crude product crosses silicagel column, obtains target product;Elemental analysis structure (molecular formula C47H30N2): it is theoretical
Value C, 90.65;H,4.86;N,4.50;Test value: C, 90.64;H,4.86;N,4.50;ESI-MS (m/z) (M+): theoretical value is
622.24 measured value 622.77.
Embodiment 4: the synthesis of compound 23:
The preparation method of compound 23 is with embodiment 3, the difference is that replacing intermediate M2-3 using intermediate M2-1.
Elemental analysis structure (molecular formula C53H35N3): theoretical value C, 89.17;H,4.94;N,5.89;Test value: C, 89.18;H,4.94;
N,5.88。ESI-MS(m/z)(M+): theoretical value 713.28, measured value 713.84.
Embodiment 5: the synthesis of compound 33:
The preparation method of compound 33 is with embodiment 3, the difference is that replacing intermediate M2-3 using intermediate M2-4.
Elemental analysis structure (molecular formula C47H30N2): theoretical value C, 90.65;H,4.86;N,4.50;Test value: C, 90.64;H,4.86;
N,4.50。ESI-MS(m/z)(M+): theoretical value 622.24, measured value 622.95.
Embodiment 6: the synthesis of compound 49:
The preparation method of compound 49 is with embodiment 2, the difference is that replacing intermediate M1-1 using intermediate M1-3.
Elemental analysis structure (molecular formula C55H36N4): theoretical value C, 87.74;H,4.82;N,7.44;Test value: C, 87.73;H,4.82;
N,7.45。ESI-MS(m/z)(M+): theoretical value 752.29, measured value 752.51.
Embodiment 7: the synthesis of compound 63:
The preparation method of compound 63 is with embodiment 2, the difference is that replacing intermediate M1-1 using intermediate M1-4.
Elemental analysis structure (molecular formula C52H37N3): theoretical value C, 88.73;H,5.30;N,5.97;Test value: C, 88.72;H,5.30;
N,5.98。ESI-MS(m/z)(M+): theoretical value 703.30, measured value 703.39.
Embodiment 8: the synthesis of compound 74:
The preparation method of compound 74 is with embodiment 3, the difference is that replacing intermediate M2-3 using intermediate M2-5.
Elemental analysis structure (molecular formula C58H41N3): theoretical value C, 89.31;H,5.30;N,5.39;Test value: C, 89.32;H,5.30;
N,5.38。ESI-MS(m/z)(M+): theoretical value 779.33, measured value 779.83.
Embodiment 9: the synthesis of compound 84:
The preparation method of compound 84 is with embodiment 3, the difference is that replacing intermediate M2-3 using intermediate M2-6.
Elemental analysis structure (molecular formula C55H35N3O): theoretical value C, 87.62;H,4.68;N,5.57;Test value: C, 87.62;H,
4.68;N,5.56.ESI-MS(m/z)(M+): theoretical value 753.28, measured value 753.52.
Embodiment 10: the synthesis of compound 92:
The preparation method of compound 92 is with embodiment 2, the difference is that replacing intermediate M1-1 using intermediate M1-7.
Elemental analysis structure (molecular formula C53H35N3): theoretical value C, 89.17;H,4.94;N,5.89;Test value: C, 89.18;H,4.94;
N,5.88。ESI-MS(m/z)(M+): theoretical value 713.28, measured value 713.68.
Embodiment 11: the synthesis of compound 98:
The preparation method of compound 98 is with embodiment 2, the difference is that replacing intermediate M1-1 using intermediate M1-8.
Elemental analysis structure (molecular formula C59H39N3): theoretical value C, 89.70;H,4.98;N,5.32;Test value: C, 89.71;H,4.98;
N,5.31。ESI-MS(m/z)(M+): theoretical value 789.31, measured value 789.66.
Embodiment 12: the synthesis of compound 105:
The preparation method of compound 105 is with embodiment 3, the difference is that replacing intermediate M2- using intermediate M2-8
1.Elemental analysis structure (molecular formula C61H39N3O): theoretical value C, 88.27;H,4.74;N,5.06;Test value: C, 88.26;H,
4.74;N,5.06.ESI-MS(m/z)(M+): theoretical value 829.31, measured value 829.92.
Embodiment 13: the synthesis of compound 115:
The preparation method of compound 115 is with embodiment 2, the difference is that replacing intermediate M1- using intermediate M1-10
1, raw material E2-2 replace raw material E2-1.Elemental analysis structure (molecular formula C64H45N3): theoretical value C, 89.79;H,5.30;N,
4.91;Test value: C, 89.78;H,5.30;N,4.92.ESI-MS(m/z)(M+): theoretical value 855.36, measured value are
855.74。
Embodiment 14: the synthesis of compound 126:
The preparation method of compound 126 is with embodiment 2, the difference is that replacing intermediate M1- using intermediate M1-11
1.Elemental analysis structure (molecular formula C64H44N4): theoretical value C, 88.45;H,5.10;N,6.45;Test value: C, 88.44;H,
5.10;N,6.46.ESI-MS(m/z)(M+): theoretical value 868.36, measured value 868.72.
Embodiment 15: the synthesis of compound 137:
The preparation method of compound 137 is with embodiment 2, the difference is that using intermediate using intermediate M1-12 replacement
Body M1-1.Elemental analysis structure (molecular formula C58H39N3O): theoretical value C, 87.74;H,4.95;N,5.29;Test value: C,
87.75;H,4.95;N,5.29.ESI-MS(m/z)(M+): theoretical value 793.31, measured value 793.55.
Embodiment 16: the synthesis of compound 144:
The preparation method of compound 144 is with embodiment 2, the difference is that replacing intermediate M1- using intermediate M1-2
1, raw material E1-2 replace raw material E1-1.Elemental analysis structure (molecular formula C41H26N2): theoretical value C, 90.08;H,4.79;N,
5.12;Test value: C, 90.08;H,4.79;N,5.13.ESI-MS(m/z)(M+): theoretical value 546.21, measured value are
546.63。
Embodiment 17: the synthesis of compound 159:
The preparation method of compound 159 is with embodiment 3, the difference is that replacing intermediate M2- using intermediate M2-1
3, raw material E2-2 replace raw material E2-1.Elemental analysis structure (molecular formula C53H35N3): theoretical value C, 89.17;H,4.94;N,
5.89;Test value: C, 89.18;H,4.94;N,5.88.ESI-MS(m/z)(M+): theoretical value 713.28, measured value are
713.68。
Embodiment 18: the synthesis of compound 169:
The preparation method of compound 169 is with embodiment 3, the difference is that intermediate M2-2 replaces intermediate M2-3, it is former
Expect that E2-2 replaces raw material E2-1.Elemental analysis structure (molecular formula C53H35N3): theoretical value C, 89.17;H,4.94;N,5.89;It surveys
Examination value: C, 89.17;H,4.94;N,5.89.ESI-MS(m/z)(M+): theoretical value 713.28, measured value 713.74.
Embodiment 19: the synthesis of compound 184:
The preparation method of compound 184 is with embodiment 3, the difference is that replacing raw material E2-1 using raw material E2-3.Member
Element analysis structure (molecular formula C48H29N3): theoretical value C, 89.00;H,4.51;N,6.49;Test value: C, 89.00;H,4.51;N,
6.49。ESI-MS(m/z)(M+): theoretical value 647.24, measured value 647.42.
Embodiment 20: the synthesis of compound 194:
The preparation method of compound 194 is with embodiment 3, the difference is that replacing intermediate M2- using intermediate M2-4
3, raw material E2-4 replace raw material E2-1.Elemental analysis structure (molecular formula C48H29N3): theoretical value C, 88.99;H,4.51;N,
6.50;Test value: C, 89.00;H,4.51;N,6.49.ESI-MS(m/z)(M+): theoretical value 647.24, measured value are
647.78。
Embodiment 21: the synthesis of compound 206:
The preparation method of compound 206 is with embodiment 2, the difference is that replacing intermediate M1- using intermediate M1-13
1, raw material E1-5 replace raw material E1-1.Elemental analysis structure (molecular formula C57H34N6): theoretical value C, 85.26;H,4.27;N,
10.47;Test value: C, 85.27;H,4.27;N,10.46.ESI-MS(m/z)(M+): theoretical value 802.28, measured value are
802.94。
Embodiment 22: the synthesis of compound 214:
The preparation method of compound 214 is with embodiment 3, the difference is that replacing intermediate M2- using intermediate M2-7
3, raw material E2-5 replace raw material E2-1.Elemental analysis structure (molecular formula C57H33N5O): theoretical value C, 85.16;H,4.14;N,
8.71;Test value: C, 85.16;H,4.14;N,8.70.ESI-MS(m/z)(M+): theoretical value 803.27, measured value are
803.92。
Embodiment 23: the synthesis of compound 221:
The preparation method of compound 221 is with embodiment 3, the difference is that replacing intermediate M2- using intermediate M2-9
3, raw material E2-3 replace raw material E2-1.Elemental analysis structure (molecular formula C59H40N4): theoretical value C, 88.03;H,5.01;N,
6.96;Test value: C, 88.04;H,5.01;N,6.95.ESI-MS(m/z)(M+): theoretical value 804.33, measured value are
804.99。
Embodiment 24: the synthesis of compound 231:
The preparation method of compound 231 is with embodiment 2, the difference is that replacing intermediate M1- using intermediate M1-10
1, raw material E1-5 replace raw material E1-1.Elemental analysis structure (molecular formula C66H43N5): theoretical value C, 87.49;H,4.78;N,
7.73;Test value: C, 87.48;H,4.78;N,7.74.ESI-MS(m/z)(M+): theoretical value 905.35, measured value are
905.59。
Embodiment 25: the synthesis of compound 239:
The preparation method of compound 239 is with embodiment 2, the difference is that replacing intermediate M1- using intermediate M1-15
1.Elemental analysis structure (molecular formula C55H38N4): theoretical value C, 87.50;H,5.07;N,7.42;Test value: C, 87.51;H,
5.07;N,7.41.ESI-MS(m/z)(M+): theoretical value 754.31, measured value 754.98.
The compounds of this invention can be used as emitting layer material use, to the compounds of this invention 7, compound 33, compound 74,
Current material CBP carries out the test of hot property, luminescent spectrum and cyclic voltammetric stability, and test result is as shown in table 2.
Table 2
Compound |
Td(℃) |
λPL(nm) |
Cyclic voltammetric stability |
Compound 7 |
420 |
469 |
It is excellent |
Compound 33 |
425 |
461 |
It is excellent |
Compound 74 |
440 |
475 |
It is excellent |
Material C BP |
353 |
369 |
Difference |
Note: thermal weight loss temperature Td is the temperature of the weightlessness 1% in nitrogen atmosphere, in the TGA-50H heat of Japanese Shimadzu Corporation
It is measured on weight analysis instrument, nitrogen flow 20mL/min;λPLIt is sample solution fluorescence emission wavelengths, opens up Pu Kang using Japan
The measurement of SR-3 spectroradiometer;Cyclic voltammetric stability be by cyclic voltammetry observe material redox characteristic come into
Row identification;Test condition: test sample is dissolved in the methylene chloride and acetonitrile mixed solvent that volume ratio is 2:1, concentration 1mg/mL, electricity
Solving liquid is the tetrabutyl ammonium tetrafluoroborate of 0.1M or the organic solution of hexafluorophosphate.Reference electrode is Ag/Ag+ electricity
Pole is titanium plate to electrode, and working electrode is ITO electrode, and cycle-index is 20 times, meets 0.9≤Ipa/Ipc≤1.1, then recycles
Volt-ampere stability is excellent, is otherwise difference, and wherein Ipa is oxidation peak current, and Ipc is reduction peak current.
By upper table data it is found that the compounds of this invention has preferable oxidation-reduction stability, higher thermal stability is closed
Suitable luminescent spectrum, so that getting a promotion using the compounds of this invention as the OLED device efficiency of emitting layer material and service life.
By the following examples 1~24 and Comparative Examples 1 and 2,3 the present invention will be described in detail synthesis compounds be used as luminescent layer in the devices
The application effect of material of main part.The structure composition of each embodiment obtained device is as shown in table 3.The test result of obtained device is shown in Table
Shown in 4.
Device embodiments 1
2/ hole injection layer of transparent substrate layer 1/ITO anode layer, 3 (molybdenum trioxide MoO3, thickness 10nm) and/hole transmission layer 4
(the weight ratio blending of compound 16 and GD19 according to 100:5, thickness the 40nm)/electronics of (TAPC, thickness 80nm)/luminescent layer 5 passes
Defeated 6 (TPBI, thickness 40nm)/electron injecting layer of layer, 7 (LiF, thickness 1nm)/cathode reflection electrode layer 8 (Al).The material being related to
Expect that structural formula is as follows:
Specific preparation process is as follows:
Transparent substrate layer 1 is transparent substrate, such as transparent PI film, glass.Ito anode layer 2 (film thickness 150nm) is carried out
Washing successively carries out neutralizing treatment, pure water, drying, then carry out ultraviolet-ozone washing to remove the transparent surface ITO
Organic residue.On having carried out the ito anode layer 2 after above-mentioned washing, using vacuum deposition apparatus, vapor deposition film thickness is 10nm
Molybdenum trioxide MoO3It is used as hole injection layer 3.And then the TAPC of 80nm thickness is deposited as hole transmission layer 4.On
After stating hole mobile material vapor deposition, the luminescent layer 5 of OLED luminescent device is made, structure includes that OLED luminescent layer 5 is made
Use material compound 49 as material of main part, for GD19 as dopant material, dopant material doping ratio is 5% weight ratio, is shone
Tunic thickness is 40nm.After above-mentioned luminescent layer 5, continuation vacuum evaporation electron transport layer materials are TPBI.The vacuum of the material
Vapor deposition film thickness is 40nm, this layer is electron transfer layer 6.On electron transfer layer 6, by vacuum deposition apparatus, making film thickness is
Lithium fluoride (LiF) layer of 1nm, this layer are electron injecting layer 7.On electron injecting layer 7, by vacuum deposition apparatus, film is made
Thickness is aluminium (Al) layer of 80nm, this layer is the use of cathode reflection electrode layer 8.After completing OLED luminescent device as described above, use
Well known driving circuit connects anode and cathode, the current efficiency of measurement device and the service life of device.
Table 3
Table 4
Illustrate: the current efficiency of comparative example 1 is 6.5cd/A (@10mA/cm2);LT95 life time decay under 5000nit brightness
For 3.8Hr.The current efficiency of comparative example 2 is 24.6cd/A (@10mA/cm2);LT95 life time decay is under 5000nit brightness
4.3Hr.The current efficiency of comparative example 3 is 25.1cd/A (@10mA/cm2);LT95 life time decay is under 5000nit brightness
7.8Hr.Life-span test system is owner of the present invention and the OLED device life-span tester that Shanghai University is studied jointly.
By the result of table 4 can be seen that compound of the present invention can be applied to OLED luminescent device production, and with than
It is compared compared with example 1,2,3, the driving service life that either efficiency or service life obtain larger change, especially device obtains biggish
It is promoted.
From the point of view of the test data provided by the embodiment, the compounds of this invention is as emitting layer material in OLED luminescent device
In have good application effect, have good industrialization prospect.The OLED device of further material preparation of the present invention exists
Efficiency is also more stable when low operating temperatures, by device embodiments 2,11,20 and device comparative example 1, comparative example 2, comparative example 3
Efficiency test is carried out in -10~80 DEG C of sections, acquired results are as shown in table 5 and Fig. 2.
Table 5
From the data of table 5 and Fig. 2 it is found that device embodiments 2,11,20 are material of the present invention and the device that known materials are arranged in pairs or groups
Part structure is compared with device comparative example 1, comparative example 2, comparative example 3, and not only Efficiency at Low Temperature is high, but also in temperature elevation process,
Efficiency steadily increases.
Although disclosing the present invention by embodiment and preferred embodiment, it should be appreciated that it is public that the present invention is not limited to institutes
The embodiment opened.On the contrary, it will be understood by those skilled in the art that it is intended to various modifications and similar arrangement.Therefore, institute
Attached the scope of the claims should be consistent with widest explanation to cover all such modifications and similar arrangement.