CN110951485B - Organic electroluminescent compound and preparation method and application thereof - Google Patents

Organic electroluminescent compound and preparation method and application thereof Download PDF

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CN110951485B
CN110951485B CN201911275402.1A CN201911275402A CN110951485B CN 110951485 B CN110951485 B CN 110951485B CN 201911275402 A CN201911275402 A CN 201911275402A CN 110951485 B CN110951485 B CN 110951485B
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马晓宇
王进政
张雪
汪康
孙毅
姚明明
王铁
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention discloses an organic electroluminescent compound, a preparation method and application thereof, wherein the molecular structural general formula of the organic electroluminescent compound is represented by formula 1:
Figure DDA0002315431330000011
wherein, in the formula 1, ar 1 ‑Ar 4 Each independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C1-C8 alkoxy, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, C1-C30 alkylamino, C6-C30 arylamino, substituted or unsubstituted C6-C30 aryl, C6-C30 aryloxy, substituted or unsubstituted C4-C12 heteroaryl; l (L) 1 ‑L 5 Each independently selected from the group consisting of a bond, a C6-C60 aryl, fluorenyl, a C3-C60 aliphatic ring, and a C2-C60 heterocyclic group. The organic electroluminescent compounds according to the inventionThe light-emitting device has high light-emitting efficiency, low driving voltage and high heat resistance, and can remarkably improve color purity and service life.

Description

Organic electroluminescent compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to an organic electroluminescent compound, a preparation method and application thereof.
Background
The organic electroluminescence phenomenon refers to a phenomenon in which electric energy is converted into light energy of an organic material. The organic EL element is a self-luminous element utilizing the following principle: by applying an electric field, the fluorescent substance emits light by the recombination energy of holes injected from the anode and electrons injected from the cathode. It has a structure of an anode, a cathode, and an organic layer interposed therebetween. In order to improve efficiency and stability of the organic EL element, the organic material layer includes a plurality of layers having different materials, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a light emitting layer, an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). Materials used as the organic material layer in the organic element may be classified into a light emitting material and a charge transporting material, for example, a hole injecting material, a hole transporting material, an electron injecting material, and the like, according to their functions.
As display sizes become larger in the portable display market, more power consumption is required, which is a very important factor in portable displays with limited battery power, and in addition, efficiency and lifetime issues. Efficiency, lifetime, driving voltage, etc. are related to each other, and the maximized efficiency cannot be obtained by simply improving the organic material layer. In addition, in order to solve the problem of light emission of the hole transport layer in the recent organic electronic element, a light emission auxiliary layer is present between the hole transport layer and the light emitting layer.
Electrons transferred from the electron transport layer to the light emitting layer and holes transferred from the hole transport layer to the light emitting layer are recombined to form excitons. However, since the material used in the hole transport layer should have a low HOMO value, it mainly has a low T1 value. Thus, excitons generated from the light emitting layer are transferred to the hole transporting layer, resulting in charge imbalance in the light emitting layer. Luminescence occurs in the hole transport layer or at the interface of the hole transport layer, so that the color purity, efficiency and lifetime of the organic electroluminescent device are reduced. Also, when a material having a rapid hole mobility is used to reduce the driving voltage, efficiency tends to be reduced. In the OLED, since hole mobility is faster than electron mobility, charge imbalance in the light emitting layer occurs, and degradation of efficiency and lifetime occurs.
It is understood that the light emitting auxiliary layer must be formed of a material capable of solving the problem of the hole transport layer, have a suitable hole mobility to provide a suitable driving voltage, a high T1 energy value and a wide bandgap. But these requirements are not met by only the core structural features with respect to the light-emitting auxiliary layer material.
Therefore, in combination with the above-mentioned problems, it is an urgent need for a solution to provide a material for a light-emitting auxiliary layer having a high T1 energy value and a wide bandgap, which can improve the efficiency and lifetime of an organic electronic device.
Disclosure of Invention
In view of the above, the present invention provides an organic electroluminescent compound, a method for preparing the same, and application thereof, and the obtained organic electroluminescent device has high luminous efficiency, low driving voltage, high heat resistance, and remarkably improved color purity and life.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
an organic electroluminescent compound having a general molecular structural formula represented by formula 1:
Figure BDA0002315431320000021
wherein, in the formula 1, ar 1 -Ar 4 Each independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C1-C8 alkoxy, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, C1-C30 alkylamino, C6-C30 arylamino, substituted or unsubstituted C6-C30 aryl, C6-C30 aryloxy, substituted or unsubstituted C4-C12 heteroaryl;
L 1 -L 5 each independently selected from the group consisting of a bond, a C6-C60 aryl group, a fluorenyl group, a C3-C60 aliphatic ring, a C2-C60 heterocyclic group.
Preferably, the Ar 1 -Ar 4 Each independently selected from C6-C12 aryl, and more preferably phenyl, biphenyl, naphthyl, fluorenyl, spirobifluorenyl, dibenzofuran, dibenzothiophene.
Preferably, the L 1 -L 5 Each independently selected from C6-C13 aryl, fluorenyl, C3-C12 heterocyclyl.
Preferably, the L 1 -L 5 Each independently selected from phenyl, deuterated phenyl, methylfluorenyl, and pyridyl.
Preferably, the Ar 1 -Ar 4 The substituent of (C) is any one or a combination of several of deuterium, halogen, silane, siloxane, boron, cyano, nitro, C1-C20 alkylthio, C1-C20 alkoxy, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl substituted by deuterium, fluorenyl, C3-C20 cycloalkyl and C7-C20 arylalkyl.
Preferably, the L 1 -L 5 Each independently substituted or unsubstituted with any one or a combination of deuterium, halogen, silyl, siloxy, boryl, cyano, nitro, C1-C20 alkylthio, C1-C20 alkoxy, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl substituted with deuterium, fluorenyl, C3-C20 cycloalkyl, C7-C20 arylalkyl.
Preferably, said formula 2 is a specific structure of formula 1.
Figure BDA0002315431320000031
Further, the compound of formula 2 may be represented by formulas 3 to 8.
Figure BDA0002315431320000041
Preferably, in the compounds of formulas 3 to 8, X 1 -X 3 May each independently be O or S.
Preferably, in the compounds of formulas 3-8, R 1 -R 6 Each independently selected from hydrogen, deuterium, halogen, cyano, nitro, hydroxy, amino; substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylamino, substituted or unsubstituted alkylthio substituted or unsubstituted C3-C60 cycloalkyl; substituted or unsubstituted C2-C60 alkenyl, substituted or unsubstituted C2-C60 alkynyl; substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C7-C60 aralkyl, substituted or unsubstituted C8-C60 aralkenyl, substituted or unsubstituted C6-C60 arylamino or substituted or unsubstituted C6-C60 arylmercapto, substituted or unsubstituted C2-C60 heteroaryl, C10-C60 fused ring group, or C10-C60 spirocyclic group.
Preferably, in the compounds of formulas 3-8, adjacent R 1 -R 6 Between and R 1 -R 6 And the substituents on the ring may be joined or condensed together to form a ring, and the ring may be a single ring or multiple rings.
Preferably, in the compounds of formulas 3-8, the ring is preferably selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl.
Preferably, in the compounds of formulas 3 to 8, each of m, p and w may be an integer of 0 to 4, and each of o, q and n may be an integer of 0 to 3.
Preferably, in the compounds of formulas 3 to 8, A 1 -A 6 Can each be independently selected from C6-C60 aryl, C3-C20 heteroarylC3-C20 cycloalkyl, C3-C20 heterocycloalkyl; phenyl and naphthyl are preferred.
Preferably, in the compounds of formulas 3-8, R 1 -R 6 Each independently substituted with any one or a combination of several of deuterium, halogen, silyl, siloxy, boryl, cyano, nitro, C1-C20 alkylthio, C1-C20 alkoxy, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, C6-C2 aryl substituted with deuterium, fluorenyl, C2-C20 heterocyclyl containing at least one heteroatom selected from O, N, S, si and P, C3-C20 cycloalkyl, C7-C20 aralkyl and C8-C20 arylalkenyl.
Preferably, the specific structural formula of the organic electroluminescent compound may be further represented as:
Figure BDA0002315431320000061
/>
Figure BDA0002315431320000071
/>
Figure BDA0002315431320000081
preferably, the halogen in the compounds of formulas 1-8 includes fluorine, chlorine, bromine or iodine.
Preferably, the alkyl groups in the compounds of formulas 1-8 include, but are not limited to, straight chain alkyl groups, branched alkyl groups, cycloalkyl groups.
Preferably, the number of carbon atoms in the compounds of formulae 1 to 8 is preferably 1 to 40.
Preferably, specific examples of the alkyl group in the compounds of formulas 1 to 8 include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, t-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, t-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl.
Preferably, the alkyl groups in the compounds of formulae 1 to 8 may be substituted.
Preferably, cycloalkyl groups in the compounds of formulas 1-8 are monocyclic, polycyclic and spiroalkyl groups.
Preferably, the cycloalkyl groups in the compounds of formulas 1-8 contain 3-12 ring carbon atoms.
Preferably, cycloalkyl groups in the compounds of formulas 1-8 include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, bicyclo [3, 1] heptyl, spiro [4,5] decyl, spiro [5,5] undecyl, adamantyl.
Preferably, the cycloalkyl groups in the compounds of formulas 1-8 may be substituted.
Preferably, the alkoxy groups in the compounds of formulas 1-8 may be linear, branched or cyclic.
Preferably, the alkoxy groups in the compounds of formulas 1-8 contain 1-40 carbon atoms.
Preferably, specific examples of the alkoxy group in the compounds of formulas 1 to 8 include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3-dimethylbutyl oxy, 2-ethylbutyl oxy, n-octoxy, n-nonoxy, n-decyloxy.
Preferably, the heterocycloalkyl group in the compounds of formulae 1-8 refers to a cycloalkyl group having at least one carbon atom replaced by a heteroatom.
Preferably, at least one heteroatom in the heterocycloalkyl group in the compounds of formulas 1-8 is selected from O, S, N, P, B, si and Se.
Preferably, at least one heteroatom in the heterocycloalkyl group in the compounds of formulas 1-8 is selected from O, S or N.
Preferably, the heterocycloalkyl group in the compounds of formulas 1-8 may be substituted.
Preferably, the alkenyl groups in the compounds of formulas 1-8 are straight chain and branched alkenyl groups.
A method for preparing an organic electroluminescent compound, the preparation of the compound of formula 1 comprising the steps of:
s1, dissolving a boric acid compound with a general formula of Sub1-1, a trihalobenzene compound with a general formula of Sub1-2, a mixture of Pd (PPh 3) 4 and K2CO3 in a mixed solvent of toluene, ethanol and water, refluxing for 12 hours, cooling the reaction solution to room temperature, extracting with dichloromethane, washing with water, drying with anhydrous MgSO4, concentrating in vacuo, and purifying the crude product by column chromatography to obtain a dihalogenated compound with a general formula of Sub 1-3;
s2, dissolving the dihalogenated compound with the general formula of Sub1-3, the boric acid compound with the general formula of Sub1-4, the mixture of Pd (PPh 3) 4 and K2CO3 obtained in the step S1 in a mixed solvent of toluene, ethanol and water, refluxing for 24 hours, cooling the reaction solution to room temperature, extracting with dichloromethane, washing with water, drying with anhydrous MgSO4, concentrating in vacuo, and purifying the crude product by column chromatography to obtain the compound with the general formula of Sub 1-5;
s3, adding tricyclohexylphosphine and Pd2 (dba) 3 into a solvent (dried 1, 4-dioxane), ventilating for 3 times, stirring for 30min at room temperature under the protection of nitrogen, adding a compound with the general formula of Sub1-5, pinacol ester of biboronate and KOAc obtained in the step S2, heating to 110 ℃, and continuously stirring for 24h; after the reaction was completed, 1, 4-dioxane was distilled off, extracted with dichloromethane and water, and the organic phase was dried over anhydrous MgSO4 and concentrated in vacuo; purifying and crystallizing the crude product by column chromatography to obtain a boron ester compound with a general formula of Sub 1;
s4, adding Pd2 (dba) 3, P (t-Bu) 3 and NaOt-Bu into a mixed solution of an amine compound with a general formula of Sub2-1 and a halogenated compound with a general formula of Sub2-2, setting the temperature to 100 ℃, and refluxing for 24 hours; extracting the solution with diethyl ether and water, drying with anhydrous MgSO4, vacuum evaporating, purifying the crude product by silica gel column, and recrystallizing to obtain amine compound with general formula of Sub 2-3;
s5, adding Pd2 (dba) 3, P (t-Bu) 3 and NaOt-Bu into the mixed solution of the amine compound with the general formula of Sub2-3 and the dihalogenated compound with the general formula of Sub2-4 obtained in the step S4, setting the temperature to be 100 ℃, and refluxing for 24 hours; extracting the solution with diethyl ether and water, drying with anhydrous MgSO4, vacuum evaporating, purifying the crude product by silica gel column, and recrystallizing to obtain halogenated amine compound with general formula of Sub 2;
s6, dissolving the obtained mixture of the boron ester compound with the general formula of Sub1 and the halogenated amine compound with the general formula of Sub2, pd (PPh 3) 4 and K2CO3 in a mixed solvent of toluene, ethanol and water, refluxing for 24 hours, cooling the reaction solution to room temperature, extracting with dichloromethane, washing with water, drying with anhydrous MgSO4, concentrating in vacuo, and purifying the crude product by column chromatography to obtain the compound shown in the formula 1.
Figure BDA0002315431320000111
Wherein Ar in the above formula 1 -Ar 4 、L 1 -L 5 Identical part representations as in formula 1 according to any one of claims 1 to 3.
Preferably, hal1, hal2, hal3 represent halogen, which may be the same or different, and when Hal2 and Hal3 represent different halogen, hal2 is more reactive than Hal3.
Preferably, the volume ratio of toluene, ethanol and water in the steps S1, S2 and S6 is 3:1:1.
The application of the organic electroluminescent compound in the organic electroluminescent device mainly comprises a first electrode, a second electrode and an organic material layer, wherein the organic material layer comprises a luminescent layer, a luminescent auxiliary layer material or a luminescent layer and a hole transport layer material, the luminescent auxiliary layer material or the hole transport layer material is composed of a compound with a molecular structural general formula represented by formula 1, and the layer thickness of the luminescent auxiliary layer or the hole transport layer is 20-25nm.
Preferably, the organic material layer comprises a single kind of the organic electroluminescent compound or a mixture of a plurality of different kinds of the organic electroluminescent compounds.
Preferably, the organic material layer is disposed between the first electrode and the light emitting layer.
Preferably, the organic material layer includes a compound represented by formulas 1 to 8.
Preferably, the light-emitting layer comprises a host material and a doping material, and the weight ratio of the host material to the doping material is 95:5.
Preferably, the organic electroluminescent compounds are used in organic light emitting devices, organic solar cells, organic photoconductors and organic transistors.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment 1 of the invention discloses an organic electroluminescent compound and a preparation method thereof, and adopts the following technical scheme:
Figure BDA0002315431320000131
s1, 20mmol of a compound having the formula Sub 1-1- (1), 20mmol of a compound having the formula Sub1-2- (1), 0.2mmol of Pd (PPh) 3 ) 4 And 60mmol of K 2 CO 3 Dissolving the mixture in a mixed solvent of 150ml toluene, 50ml ethanol and 50ml water, refluxing for 24 hours, cooling the reaction solution to room temperature, extracting with dichloromethane, washing with water, and concentrating with anhydrous MgSO 4 Drying, vacuum concentrating, purifying the crude product by column chromatography to give a compound of the general formula Sub1-3- (1)7.6g of compound, yield 85%;
s2, taking 16mmol of the compound with the general formula of Sub1-3- (1) obtained in the step S1, 16mmol of the compound with the general formula of Sub1-4- (1), and 0.16mmol of Pd (PPh) 3 ) 4 And 48mmol of K 2 CO 3 Dissolving the mixture in a mixed solvent of 150ml toluene, 50ml ethanol and 50ml water, refluxing for 24 hours, cooling the reaction solution to room temperature, extracting with dichloromethane, washing with water, and concentrating with anhydrous MgSO 4 Drying, vacuum concentrating, purifying the crude product by column chromatography to obtain compound of general formula Sub1-5- (1), 8.04g, yield 80%;
s3, tricyclohexylphosphine and 0.12mmol of Pd 2 (dba) 3 Adding 300ml of solvent (dried 1, 4-dioxane), ventilating for 3 times, stirring at room temperature under the protection of nitrogen for 30min, adding 12.0mmol, 13.2mmol and 36.0mmol of KOAc of the compound with the general formula of Sub1-5- (1) obtained in the step S2, heating to 110 ℃, and continuously stirring for 24h; after the reaction was completed, 1, 4-dioxane was distilled off, extracted with methylene chloride and water, and dried over anhydrous MgSO 4 Drying the organic phase and concentrating in vacuum; purifying and crystallizing the crude product by column chromatography to obtain a compound of general formula Sub1- (1), 7.35g, yield 85%;
s4 to a mixed solution of 20mmol of the compound having the formula Sub2-1- (1) and 20mmol of the compound having the formula Sub2-2- (1) was added 0.2mmol of Pd 2 (dba) 3 PPh of 2mmol 3 And 60mmol NaOt-Bu, the temperature is set to 100 ℃, and the reflux is carried out for 24 hours; extracting the solution with diethyl ether and water, extracting with anhydrous MgSO 4 Drying, vacuum evaporation, purification of the crude product by silica gel column and recrystallization gave a compound of general formula Sub2-3- (1), 2.8g, yield 83%;
s5, adding 0.16mmol of Pd to a mixed solution of 16mmol of the compound having the general formula of Sub2-3- (1) and 17mmol of the compound having the general formula of Sub2-4- (1) obtained in the step S4 2 (dba) 3 PPh of 1.6mmol 3 And 48mmol of NaOt-Bu, the temperature is set to 100 ℃, and the reflux is carried out for 24 hours; the solution was extracted with diethyl ether and water, dried over anhydrous MgSO4, evaporated in vacuo, and the crude product purified by a silica gel column and recrystallized4.13g of a compound of the formula Sub2- (1) was obtained in 80% yield;
s6 Pd (PPh) in the form of 1.0eq of the compound of the formula Sub1 and 1.1eq of the compound of Sub2, 0.01eq 3 ) 4 And 3.0eq of K 2 CO 3 Adding the mixture of (C) into a toluene/ethanol/water mixed solvent, refluxing for 24 hours, separating the solution, extracting the aqueous phase with diethyl ether and water, mixing the organic phases, and using anhydrous MgSO 4 Drying, evaporation, purification of the crude product by column on silica gel and recrystallization gave the final product compound 1,8.54g in 85% yield.
Specific structures of the synthesized Sub1- (1) include, but are not limited to, the following table 1, and mass spectrum data thereof are shown in table 2.
TABLE 1
Figure BDA0002315431320000151
/>
Figure BDA0002315431320000161
TABLE 2
Compounds of formula (I) FD-MS
Sub 1-(1) m/z＝720.17(C 48 H 37 BO 2 S 2 ＝720.23)
Sub 1-(7) m/z＝720.29(C 48 H 37 BO 2 S 2 ＝720.23)
Sub 1-(10) m/z＝688.42(C 48 H 37 BO 4 ＝688.28)
Sub 1-(20) m/z＝628.19(C 42 H 33 BO 3 S＝628.22)
Sub 1-(21) m/z＝628.71(C 42 H 33 BO 3 S＝628.22)
Sub 1-(34) m/z＝643.97(C 42 H 33 BO 2 S 2 ＝644.20)
Sub 1-(39) m/z＝628.35(C 42 H 33 BO 3 S＝628.22)
Sub 1-(41) m/z＝462.07(C 30 H 27 BO 2 S＝462.18)
Sub 1-(49) m/z＝578.83(C 39 H 35 BO 2 S＝578.25)
Sub 1-(55) m/z＝598.31(C 42 H 35 BO 3 ＝598.27)
Specific structures of the synthesized Sub2- (1) include, but are not limited to, the following table 3, and mass spectrum data thereof are shown in table 4.
TABLE 3 Table 3
Figure BDA0002315431320000171
/>
Figure BDA0002315431320000181
TABLE 4 Table 4
Compounds of formula (I) FD-MS
Sub 2-(1) m/z＝323.8(C18H14BrN＝323.03)
Sub 2-(7) m/z＝339.62(C 48 H 37 BO 2 S 2 ＝399.06)
Sub 2-(10) m/z＝439.77(C27H22BrN＝439.09)
Sub 2-(17) m/z＝475.11(C30H22BrN＝475.09)
Sub 2-(20) m/z＝373.21(C22H16BrN＝373.05)
Sub 2-(25) m/z＝489.57(C30H20BrNO＝489.07)
Sub 2-(39) m/z＝489.23(C30H20BrNO＝489.07)
Sub 2-(41) m/z＝505.08(C30H20BrNS＝505.05)
Sub 1-(55) m/z＝565.71(C36H24BrNO＝565.10)
Specific structures of the synthesized intermediates and final products include, but are not limited to, table 5 below, with mass spectral data as shown in table 6.
TABLE 5
Figure BDA0002315431320000182
/>
Figure BDA0002315431320000191
/>
Figure BDA0002315431320000201
TABLE 6
Compounds of formula (I) FD-MS
1 m/z＝837.55(C 60 H 39 NS 2 ＝837.25)
7 m/z＝913.01(C 66 H 43 NS 2 ＝913.28)
10 m/z＝921.37(C 69 H 47 NO 2 ＝921.36)
17 m/z＝912.81(C 66 H 43 NS 2 ＝913.28)
20 m/z＝795.42(C 58 H 37 NOS＝795.26)
21 m/z＝821.64(C 60 H 39 NOS＝821.28)
25 m/z＝971.25(C 72 H 45 NO 3 ＝971.34)
34 m/z＝927.62(C 66 H 41 NOS 2 ＝927.26)
39 m/z＝911.67(C 66 H 41 NO 2 S＝911.29)
41 m/z＝761.19(C 54 H 35 NS 2 ＝761.22)
49 m/z＝877.78(C 63 H 43 NS 2 ＝877.28)
55 m/z＝957.27(C 72 H 47 NO 2 ＝957.36)
Example 2
The embodiment 2 of the invention discloses application of an organic electroluminescent compound in an organic electroluminescent device, and a preparation method of the organic electroluminescent device adopts the following technical scheme:
device example (1): manufacture of organic electroluminescent device containing Compound 1, the final product of example 1
The thickness of the coating is equal to
Figure BDA0002315431320000211
The ITO glass substrate is washed for 2 times in distilled water for 30 minutes by ultrasonic wave, repeatedly washed for 2 times by distilled water for 10 minutes by ultrasonic wave, and after the distilled water is washed, solvents such as isopropanol, acetone, methanol and the like are washed by ultrasonic wave in sequence, dried and transferred into a plasma washer, and the substrate is washed for 5 minutes and then is sent into a vapor deposition machine. Evaporating 4,4' -tris [ 2-naphthylphenylamino with a thickness of 30nm on the prepared ITO transparent electrode]Triphenylamine (2-TNATA) was used as the hole injection layer. Then, the compound 1 was vacuum-evaporated on the formed hole injection layer to form a hole transport layer having a thickness of 20 nm. Then 4,4'-N, N' -biphenyl dicarbazole ("CBP") with the thickness of 20nm and a doping material Ir (bty) 2acac are evaporated on the hole transport layer. The weight ratio of host material to dopant material was 95:5. Then, TPBi with a thickness of 30nm was vacuum deposited as a hole blocking layer and an electron transport layer on the light emitting layer. Lithium fluoride (LiF) having a thickness of 0.5nm was vacuum-deposited on the electron transport layer as an electron injection layer. Finally, aluminum with the thickness of 100nm is evaporated to serve as a cathode, so that the preparation of the organic electroluminescent device is completed. And testing the performance luminescence characteristics of the obtained device.
Device example (2) -device example (12):
the organic electroluminescent devices containing the compounds 7, 10, 17, 20, 21, 25, 34, 41, 49 and 55 were produced by replacing the compound 1 as the organic electroluminescent compound in the device example (1) with the compounds 7, 10, 17, 20, 21, 25, 34, 39, 41, 49 and 55, respectively, in the same manner.
Device comparative example (1): an organic electroluminescent device containing comparative compound 1 was manufactured. An organic electroluminescent device containing comparative compound 1 was fabricated in the same manner as in device example (1) except that the material of the hole transport layer was replaced with comparative compound 1 from compound 1.
Device comparative example (2): an organic electroluminescent device containing comparative compound 2 was manufactured. An organic electroluminescent device containing comparative compound 2 was produced in the same manner as in device example (1) except that the material of the hole transport layer was replaced with comparative compound 2 from compound 1.
Figure BDA0002315431320000212
Figure BDA0002315431320000221
Table 7 shows the results of testing the luminescence characteristics (luminance value: 5000 cd/m) of the organic electroluminescent devices prepared in the device example (1) -device example (12) and the device comparative examples (1) and (2) according to the present invention 2 )。
TABLE 7
Figure BDA0002315431320000222
As can be seen from table 7, the organic electroluminescent device prepared using the compound provided by the present invention as a hole transport layer material has significantly reduced driving voltage and current density, and significantly improved luminous efficiency and lifetime, as compared to the organic electroluminescent device prepared using comparative compound 1 and comparative compound 1 as hole transport materials.
Device example (13)
The thickness of the coating is equal to
Figure BDA0002315431320000231
The ITO glass substrate is washed for 2 times in distilled water for 30 minutes by ultrasonic wave, repeatedly washed for 2 times by distilled water for 10 minutes by ultrasonic wave, and after the distilled water is washed, solvents such as isopropanol, acetone, methanol and the like are washed by ultrasonic wave in sequence, dried and transferred into a plasma washer, and the substrate is washed for 5 minutes and then is sent into a vapor deposition machine. Evaporating 4,4' -tris [ 2-naphthylphenylamino ] with a thickness of 50nm on the prepared ITO transparent electrode]Triphenylamine (2-TNATA) was used as the hole injection layer. Then NPB was vacuum evaporated on top of the formed hole injection layer to a thickness of 50 nm. Evaporating a compound 1 with the thickness of 20nm on the hole transport layer to serve as a light-emitting auxiliary layer; 4,4'-N, N' -biphenyldicarbazole ("CBP") and a doping material Ir (ppy) 3 were then evaporated on the above-mentioned light-emitting auxiliary layer to a thickness of 20 nm. The weight ratio of host material to dopant material was 97:3. Then, TPBi with a thickness of 30nm was vacuum deposited as a hole blocking layer and an electron transport layer on the light emitting layer. Lithium fluoride (LiF) having a thickness of 0.5nm was vacuum-deposited on the electron transport layer as an electron injection layer. Finally, aluminum with the thickness of 100nm is evaporated to serve as a cathode, so that the preparation of the organic electroluminescent device is completed.
Device example (14) -device example (24)
An organic electroluminescent device containing compounds 7, 10, 17, 20, 21, 25, 34, 41, 49 and 55 was produced by replacing compound 1 of the light-emitting auxiliary layer in device example (13) with compounds 7, 10, 17, 20, 21, 25, 34, 39, 41, 49 and 55, respectively, in the same manner.
Device comparative example (3): an organic electroluminescent device containing comparative compound 2 was manufactured. An organic electroluminescent device containing comparative compound 2 was produced in the same manner as in device example (13) except that compound 1 of the light-emitting auxiliary layer was replaced with comparative compound 2.
Device comparative example (4): device comparative example (3) was produced in the same manner as in device example (13). Except that the light-emitting auxiliary layer is not contained.
Table 8 shows the results of testing the luminescence characteristics (luminance value: 5000 cd/m) of the organic electroluminescent devices prepared in the device example (13) -device example (24) and the device comparative examples (3) and (4) according to the present invention 2 )。
TABLE 8
Figure BDA0002315431320000232
Figure BDA0002315431320000241
As can be seen from table 8, the organic electroluminescent device prepared using the compound provided by the present invention as a light-emitting auxiliary layer material has significantly reduced driving voltage and current density, and significantly improved light-emitting efficiency and lifetime, compared to the organic electroluminescent device using comparative compound 2 as a light-emitting auxiliary layer material and no light-emitting auxiliary layer.
It will be apparent to those skilled in the art that many modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. It is therefore contemplated that the present invention cover the modifications and variations of the invention provided they come within the scope of the appended claims and their equivalents.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (5)

1. An organic electroluminescent compound, characterized in that the specific structural formula of its molecular structure is represented by:
Figure FDA0004174366710000011
/>
Figure FDA0004174366710000021
2. a method of preparing an organic electroluminescent compound as claimed in claim 1, wherein preparing the compound comprises the steps of:
s1, boric acid compound with general formula of Sub1-1, trihalogenobenzene compound with general formula of Sub1-2 and Pd (PPh) 3 ) 4 And K 2 CO 3 Dissolving the mixture in a mixed solvent of toluene, ethanol and water, refluxing for 12h, cooling the reaction solution to room temperature, extracting with dichloromethane, washing with water, and concentrating with anhydrous MgSO 4 Drying, vacuum concentrating, purifying the crude product by column chromatography to obtain dihalo compound of general formula Sub 1-3;
s2, dihalogenated compound with general formula of Sub1-3, boric acid compound with general formula of Sub1-4 and Pd (PPh) obtained in step S1 3 ) 4 And K 2 CO 3 Dissolving the mixture in a mixed solvent of toluene, ethanol and water, refluxing for 24 hours, cooling the reaction solution to room temperature, extracting with dichloromethane, washing with water, and concentrating with anhydrous MgSO 4 Drying, vacuum concentrating, purifying the crude product by column chromatography to obtain a compound of general formula Sub 1-5;
s3, tricyclohexylphosphine and Pd 2 (dba) 3 Adding solvent (dried 1, 4-dioxane), ventilating for 3 times, stirring at room temperature under nitrogen protection for 30min, adding compound with general formula of Sub1-5 obtained in step S2, pinacol ester of biboronate, and KOAc, heating to 110deg.C, and continuously stirring for 24 hr; after the completion of the reaction, 1, 4-dioxane was distilled off, extracted with methylene chloride and water, and dried over anhydrous MgSO 4 Drying the organic phase and concentrating in vacuum; purifying and crystallizing the crude product by column chromatography to obtain a boron ester compound with a general formula of Sub 1;
s4, adding Pd into the mixed solution of the amine compound with the general formula of Sub2-1 and the halogenated compound with the general formula of Sub2-2 2 (dba) 3 、P(t-Bu) 3 And NaOt-Bu is set at 100 ℃ and refluxed for 24 hours; extracting the solution with diethyl ether and water, extracting with anhydrous MgSO 4 Drying, evaporating in vacuum, purifying the crude product by a silica gel column, and recrystallizing to obtain an amine compound with a general formula of Sub 2-3;
s5, adding Pd into the mixed solution of the amine compound with the general formula of Sub2-3 and the dihalo compound with the general formula of Sub2-4 obtained in the step S4 2 (dba) 3 、P(t-Bu) 3 And NaOt-Bu, setting the temperature to 100 ℃, and refluxing for 24 hours; extracting the solution with diethyl ether and water, extracting with anhydrous MgSO 4 Drying, evaporating in vacuum, purifying the crude product by a silica gel column, and recrystallizing to obtain a halogenated amine compound with a general formula of Sub 2;
s6, mixing the boron ester compound with formula Sub1, halogenated amine compound with Sub2, pd (PPh) 3 ) 4 And K 2 CO 3 Dissolving the mixture in a mixed solvent of toluene, ethanol and water, refluxing for 24 hours, cooling the reaction solution to room temperature, extracting with dichloromethane, washing with water, and concentrating with anhydrous MgSO 4 Drying, vacuum concentrating, purifying the crude product by column chromatography to obtain the compound;
Figure FDA0004174366710000041
wherein,,ar in the above 1 -Ar 4 、L 1 -L 5 Identical moiety representations are identical to those in the compounds of claim 1.
3. The method for preparing an organic electroluminescent compound according to claim 2, wherein the volume ratio of toluene, ethanol and water in the steps S1, S2 and S6 is 3:1:1.
4. Use of an organic electroluminescent compound as claimed in claim 1 in an organic electroluminescent device, characterized in that the organic electroluminescent device essentially comprises a first electrode, a second electrode, an organic material layer comprising a luminescent layer, a luminescent auxiliary layer material or comprising a luminescent layer, a hole transport layer material, the luminescent auxiliary layer material or the hole transport layer material being a compound as claimed in claim 1, the luminescent auxiliary layer or the hole transport layer having a layer thickness of 20-25nm.
5. The use of an organic electroluminescent compound according to claim 4, wherein the light-emitting layer comprises a host material and a dopant material, wherein the weight ratio of the host material to the dopant material is 95:5.
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