CN110272427B - Compound with fluorene as core, preparation method thereof and application thereof in organic electroluminescent device - Google Patents

Compound with fluorene as core, preparation method thereof and application thereof in organic electroluminescent device Download PDF

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CN110272427B
CN110272427B CN201810942255.8A CN201810942255A CN110272427B CN 110272427 B CN110272427 B CN 110272427B CN 201810942255 A CN201810942255 A CN 201810942255A CN 110272427 B CN110272427 B CN 110272427B
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fluorene
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庞羽佳
唐丹丹
张兆超
李崇
王芳
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Jiangsu Sunera Technology Co Ltd
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Abstract

The invention relates to an organic compound taking fluorene as a core, a preparation method thereof and application thereof in an organic electroluminescent device, wherein the structure of the compound is that the fluorene is connected with a dibenzo five-membered ring parallel structure through a carbon-carbon bond, the carbon-carbon bond connection not only improves the chemical stability of the material, but also avoids the exposure of the active position of a branched chain group, and the whole molecule is a larger rigid structure and has a high triplet state energy level (T1); the steric hindrance is large, the rotation is not easy, and the three-dimensional structure is more stable, so that the compound has higher glass transition temperature and molecular thermal stability; in addition, the HOMO and LUMO distribution positions of the compound are separated from each other, so that the compound has proper HOMO and LUMO energy levels; therefore, after the compound is applied to an OLED device, the luminous efficiency of the device can be effectively improved, and the service life of the device can be effectively prolonged.

Description

Compound with fluorene as core, preparation method thereof and application thereof in organic electroluminescent device
Technical Field
The invention relates to the technical field of semiconductors, in particular to an organic compound taking fluorene as a core, a preparation method thereof and application thereof in an organic electroluminescent device.
Background
The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has a very wide application prospect. The OLED light-emitting device is like a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and various different functional materials are mutually overlapped together according to purposes to form the OLED light-emitting device. When voltage is applied to electrodes at two ends of the OLED light-emitting device and positive and negative charges in the organic layer functional material film layer are acted through an electric field, the positive and negative charges are further compounded in the light-emitting layer, and OLED electroluminescence is generated.
Currently, the OLED display technology is already applied in the fields of smart phones, tablet computers, and the like, and is further expanded to the large-size application field of televisions, and the like, but compared with the actual product application requirements, the performance of the OLED device, such as light emitting efficiency, service life, and the like, needs to be further improved. Current research into improving the performance of OLED light emitting devices includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the photoelectric functional material of the OLED are required to create the functional material of the OLED with higher performance.
The photoelectric functional materials of the OLED applied to the OLED device can be divided into two categories from the aspect of application, namely charge injection transmission materials and luminescent materials. Further, the charge injection transport material may be classified into an electron injection transport material, an electron blocking material, a hole injection transport material, and a hole blocking material, and the light emitting material may be classified into a host light emitting material and a doping material.
In order to fabricate a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric properties, for example, as a charge transport material, good carrier mobility, high glass transition temperature, etc. are required, as a host material of a light-emitting layer, good bipolar, appropriate HOMO/LUMO energy level, etc. are required.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, the OLED device structure applied in industry comprises a hole injection layer, a hole transmission layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transmission layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transmission material, a light emitting material, an electron transmission material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional material has stronger selectivity, and the performance of the same material in the devices with different structures can be completely different.
Therefore, aiming at the industrial application requirements of the current OLED device and the requirements of different functional film layers and photoelectric characteristics of the OLED device, a more suitable OLED functional material or material combination with higher performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual demand of the current OLED display lighting industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and it is very important to develop a higher-performance organic functional material as a material enterprise.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an organic compound taking fluorene as a core and application thereof in an organic electroluminescent device. The compound contains a fluorene structure, has higher glass transition temperature and molecular thermal stability, proper HOMO and LUMO energy levels and higher Eg, and can effectively improve the photoelectric property of an OLED device and the service life of the OLED device through device structure optimization.
The technical scheme of the invention is as follows:
a compound taking fluorene as a core has a structure shown as a general formula (1):
Figure BDA0001769358100000021
wherein L represents a single bond, substituted or unsubstituted C6-60One of arylene and substituted or unsubstituted 5-to 60-membered heteroarylene containing one or more heteroatoms, wherein the heteroatoms are N, O or S;
Ar1、Ar2each independently represents substituted or unsubstituted C6-60One of an aryl, a substituted or unsubstituted 5-60 membered heteroaryl containing one or more heteroatoms which is N, O or S;
r represents a structure represented by the general formula (2);
Figure BDA0001769358100000022
in the general formula (2), X1Represented as O or S;
c in general formula (1)L1-CL2Key, CL2-CL3Bond or CL3-CL4The attachment site of the bond.
Further, Ar1Is shown as D, F, C1-10Phenyl group, D, F, C, substituted or not by straight or branched alkyl groups1-10Biphenyl radical, D, F, C, substituted or unsubstituted by a linear or branched alkyl radical1-10Straight or branched chain alkyl substituted or unsubstituted terphenyl group, D, F, C1-10Straight or branched chain alkyl substituted or unsubstituted naphthyl, D, F, C1-10A linear or branched alkyl substituted or unsubstituted pyridylene group, a structure represented by general formula (3) or general formula (4):
Figure BDA0001769358100000023
wherein, X2Is represented by O, S, N, C (R)1)(R2) Or N (R)3)；
L1Represented by phenylene, biphenylene, naphthylene, terphenylene or pyridylene; l is2Represents a single bond, phenylene, biphenylene, naphthylene, terphenylene or pyridylene;
z represents a nitrogen atom or C-R4(ii) a And Z at the attachment site is represented as a carbon atom;
R1to R3Are each independently represented by C1-20Alkyl, substituted or unsubstituted C6-30One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; r1And R2Not forming a ring or connecting the rings;
the R is4Represented by hydrogen atom, fluorine atom, cyano group, C1-20Alkyl of (C)2-20Alkenyl of (a), substituted or unsubstituted C6-30One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; two or more adjacent R4Do not form a ring or bond to each other to form a ring;
the substituents of the above-mentioned substituted radicals being optionally selected from halogen, cyano, C1-20Alkyl of (C)6-30One or more of an aryl group, a 5-to 30-membered heteroaryl group containing one or more heteroatoms;
the hetero atom in the heteroaryl is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
Further, L is represented as D, F, C1-10Linear or branched alkyl substituted or unsubstituted phenylene D, F, C1-10D, F, C A straight or branched chain alkyl substituted or unsubstituted biphenylene1-10Linear or branched alkyl substituted or unsubstituted pyridylene D, F, C1-10Linear or branched alkyl substituted or unsubstituted pyrimidinylene, D, F, C1-10Pyridazinyl radicals, D, F, C, substituted or not by straight or branched alkyl radicals1-10Straight or branched chain alkyl substituted or unsubstituted pyrazinylene radical or D, F, C1-10One of linear or branched alkyl substituted or unsubstituted triazinylene; ar (Ar)2Is shown as D, F, C1-10Straight chainOr a branched alkyl substituted or unsubstituted phenyl, D, F, C1-10Straight or branched chain alkyl substituted or unsubstituted biphenylyl D, F, C1-10Straight or branched chain alkyl substituted or unsubstituted terphenyl group, D, F, C1-10Straight or branched chain alkyl substituted or unsubstituted naphthyl, D, F, C1-10Straight or branched chain alkyl substituted or unsubstituted anthracenyl group, D, F, C1-10Linear or branched alkyl substituted or unsubstituted phenanthryl D, F, C1-10Linear or branched alkyl substituted or unsubstituted pyrenyl, D, F, C1-10Linear or branched alkyl substituted or unsubstituted pyridyl D, F, C1-10Linear or branched alkyl substituted or unsubstituted pyrimidyl, D, F, C1-10Pyridazinyl radicals, D, F, C, substituted or not by straight or branched alkyl radicals1-10Pyrazinyl, D, F, C, substituted or unsubstituted by straight or branched alkyl groups1-10One of a linear or branched alkyl substituted or unsubstituted triazinyl group;
the R is1～R3Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl or pyridyl;
the R is4Each occurrence, identically or differently, is represented by a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group, a benzofuranyl group, a carbazolyl group, a benzothienyl group or a furanyl group;
the substituent of the substitutable group is one or more selected from fluorine atom, cyano, methyl, ethyl, propyl, isopropyl, tert-butyl, amyl, phenyl, naphthyl, biphenyl, pyridyl, benzofuryl, carbazolyl, benzothienyl or furyl.
Further, in the general formula (1)
Figure DEST_PATH_2
Expressed as:
Figure BDA0001769358100000032
Figure BDA0001769358100000041
Figure BDA0001769358100000042
any one of them.
Further, the specific structural formula of the compound is as follows:
Figure BDA0001769358100000043
Figure BDA0001769358100000051
Figure BDA0001769358100000061
Figure BDA0001769358100000071
Figure BDA0001769358100000081
Figure BDA0001769358100000091
Figure BDA0001769358100000101
Figure BDA0001769358100000111
Figure BDA0001769358100000121
Figure BDA0001769358100000131
Figure BDA0001769358100000141
Figure BDA0001769358100000151
Figure BDA0001769358100000161
Figure BDA0001769358100000171
Figure BDA0001769358100000181
any one of them.
In another aspect of the present invention, there is provided a process for preparing a compound as described above, comprising the steps of: dissolving intermediate I and intermediate II in mixed solvent of toluene and ethanol, adding Na2CO3Aqueous solution and Pd (PPh)3)4(ii) a Reacting the mixed solution of the reactants at 90-110 ℃ for 10-24h under an inert atmosphere, cooling, filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing the residue through a silica gel column to obtain a target product;
the reaction equation occurring during the preparation process is:
Figure BDA0001769358100000182
further, the volume ratio of the toluene to the ethanol is 1.5-3: 1; the molar ratio of the intermediate I to the intermediate II is 1: 1.0-1.5; pd (C)PPh3)4The molar ratio of the intermediate I to the intermediate I is 0.006-0.02: 1; na (Na)2CO3The molar ratio of the intermediate I to the intermediate I is 2.0-3.0: 1.
Further, the preparation method of the intermediate I comprises the following steps:
step 1: dissolving raw materials U and Mg powder by using dry Tetrahydrofuran (THF), and adding a catalyst I in an inert atmosphere2Heating to 40 ℃, stirring until the solution turns from yellow to colorless, heating the mixed solution to 60-90 ℃, stirring for reacting for 3-5 hours until no magnesium powder remains, and generating a Grignard reagent intermediate V after the reaction is finished;
step 2: dissolving 9-fluorenone in dry THF, dropwise adding the Grignard reagent intermediate V in an inert atmosphere, reacting the obtained mixed solution at 60-90 ℃ for 10-24h while stirring to generate a large amount of white precipitate, cooling to room temperature, and adding saturated NHCl4Converting the grignard salt to an alcohol; after the reaction is finished, extracting with diethyl ether, drying, carrying out rotary evaporation, and passing the residue through a silica gel column to obtain a yellowish solid tertiary alcohol intermediate W;
and step 3: dissolving the intermediate W with toluene, slowly dropwise adding 48% HBr aqueous solution into the mixed solution, stirring and reacting at 20-25 ℃ for 15-30h, separating liquid after the reaction is finished, extracting a water phase with toluene, combining organic phases, drying with anhydrous sodium sulfate, performing suction filtration, washing a filter cake with ethyl acetate, performing rotary evaporation on the filtrate and the washing liquid until no solvent exists, and passing the residue through a silica gel column to obtain an intermediate I;
the reaction equation occurring during the preparation is as follows:
Figure BDA0001769358100000183
Figure BDA0001769358100000191
further, the molar ratio of the raw material U to Mg is 1: 1.0-1.2; i is2The mol ratio of the raw material U to the raw material U is 0.006-0.02: 1; moles of said 9-fluorenone to intermediate VThe ratio is 1: 1.0-1.2; the volume of 48% aqueous HBr was 20mL/0.01mol of intermediate W.
Further, the preparation method of the intermediate II comprises the following steps:
step 1: dissolving the raw material A and the raw material B by using a toluene-ethanol mixed solvent with a volume ratio of 1.5-3.0: 1, and adding Na2CO3Aqueous solution, Pd (PPh)3)4(ii) a Under the protection of nitrogen, stirring the mixed solution at 95-100 ℃ for reaction for 10-24h, then cooling to room temperature, filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing the residue through a silica gel column to obtain an intermediate S1;
step 2: under the protection of nitrogen, dissolving the intermediate S1 in o-dichlorobenzene, adding triphenylphosphine, stirring and reacting at 170-190 ℃ for 12-16 h, cooling to room temperature after the reaction is finished, filtering, carrying out reduced pressure rotary evaporation on the filtrate, and passing the residue through a neutral silica gel column to obtain an intermediate S2;
and step 3: under the protection of nitrogen, sequentially adding the intermediate S2, the raw material C, sodium tert-butoxide and Pd2(dba)3Dissolving tri-tert-butylphosphine in toluene, heating to 110-120 ℃, performing reflux reaction for 12-24 hours, and sampling a sample point plate to show that the reaction is complete when no intermediate S2 remains; naturally cooling to room temperature, filtering, carrying out reduced pressure rotary distillation on the filtrate until no fraction is produced, and passing the residue through a neutral silica gel column to obtain an intermediate S3;
and 4, step 4: dissolving the intermediate S3 in acetic acid, and cooling to 0 ℃ by using an ice salt bath; dissolving liquid bromine in glacial acetic acid, slowly dropwise adding the solution into an acetic acid solution of the intermediate S3, stirring at room temperature for 5 hours, and sampling a sample point plate to show that the reaction is complete when no intermediate S3 remains; after the reaction is finished, adding alkali liquor into the reaction liquid for neutralization, extracting by using dichloromethane, layering, taking an organic phase for filtration, decompressing and rotary-steaming the filtrate until no fraction is produced, and passing through a silica gel column to obtain an intermediate S4;
and 5: under the protection of nitrogen, dissolving an intermediate S4 in tetrahydrofuran, cooling to-78 ℃, adding 1.6mol/L tetrahydrofuran solution of n-butyllithium into a reaction system, reacting at-78 ℃ for 3h, adding triisopropyl borate, reacting for 2h, raising the temperature of the reaction system to 0 ℃, adding 2mol/L hydrochloric acid solution, stirring for 3h, completely reacting, adding diethyl ether for extraction, adding anhydrous magnesium sulfate into an extract liquid, drying, performing rotary evaporation, and recrystallizing by using an ethanol solvent to obtain an intermediate II;
the reaction equation occurring during the preparation is as follows:
Figure BDA0001769358100000192
further, the molar ratio of the raw material B to the raw material A is 1: 1.5-3.0; pd (PPh)3)4The molar ratio of the raw material B to the raw material B is 0.006-0.02: 1, and Na2CO3The molar ratio of the raw material B to the raw material B is 2.0-3.0: 1; the molar ratio of the intermediate S1 to triphenylphosphine is 1: 1-2; the molar ratio of the intermediate S2 to the raw material C is 1: 1-2; the Pd2(dba)3The molar ratio of the intermediate S2 to the tri-tert-butylphosphine is 0.006-0.02: 1, and the molar ratio of the tri-tert-butylphosphine to the intermediate S2 is 0.006-0.02: 1; the molar ratio of the sodium tert-butoxide to the intermediate S2 is 2.0-3.0: 1; the molar ratio of the intermediate S3 to the liquid bromine is 1: 1-1.5; the molar ratio of the intermediate S4 to n-butyllithium is 1: 1-1.5; the molar ratio of the intermediate S4 to triisopropyl borate is 1: 1-1.5.
The invention also provides application of the fluorene-core compound in preparation of an organic electroluminescent device.
The invention also provides an organic electroluminescent device which comprises at least one functional layer, wherein the material used by the functional layer contains the compound taking fluorene as the core.
The invention also provides an organic electroluminescent device which comprises the electron blocking layer, wherein the electron blocking layer is made of the material containing the compound taking fluorene as the core.
The invention also provides an organic electroluminescent device which comprises a luminescent layer, wherein the luminescent layer is made of a material containing the fluorene-based compound.
The beneficial technical effects of the invention are as follows:
1. the compound of the invention takes fluorene as a framework and is connected with a dibenzo five-membered ring fused ring structure by a carbon-carbon bond, and the carbon-carbon bond connection not only improves the stability of the material, but also avoids the exposure of the active position of a branched chain group; besides the higher rigidity of fluorene, the dibenzo five-membered ring fused ring structure is also a large pi bond conjugated rigid structure, has high steric hindrance and is not easy to rotate, so that the three-dimensional structure of the compound material is more stable. And the spin density distribution of the triplet state energy level T1 of the compound is basically on a branch chain, and the branch chain has a high T1 energy level, so that the compound also has a high T1 energy level. When the compound is used as an electron blocking layer material of an OLED, the high T1 energy level can effectively block energy from being transferred from a light emitting layer to a hole transport layer, energy loss is reduced, and the energy of a main material of the light emitting layer is fully transferred to a doping material, so that the light emitting efficiency of the material applied to a device is improved.
2. The structure of the compound enables the distribution of electrons and holes in the luminescent layer to be more balanced, and under the proper HOMO energy level, the hole injection and transmission performance is improved; under a proper LUMO energy level, the organic electroluminescent material plays a role in blocking electrons, and improves the recombination efficiency of excitons in the luminescent layer; when the fluorene modified fluorene branched fluorene has high in has high efficiency, high current.
3. The branched chain structure of the compound contains O or S atoms, so that the branched chain group presents weak electric absorption, and after the compound is prepared into an OLED device, the compound is beneficial to dredging redundant electrons transmitted from a light emitting layer, reducing the influence of negative charges on materials or the device, reducing the leakage current generated by the device and further prolonging the service life of the OLED device.
4. When the compound is applied to an OLED device, high film stability can be kept through device structure optimization, the photoelectric performance of the OLED device and the service life of the OLED device can be effectively improved, and the compound has good application effect and industrialization prospect.
Drawings
FIG. 1 is a schematic diagram of the application of the compounds of the present invention to an OLED device;
FIG. 2 is a graph of current efficiency measured at different temperatures for OLED devices prepared with the compounds of the present invention.
Fig. 3 is a graph showing reverse voltage leakage current test curves of the devices manufactured in example 1 and comparative example 1.
Description of reference numerals: 1-a transparent substrate layer; 2-an ITO anode layer; 3-a hole injection layer; 4-a hole transport layer; 5-a hole transporting/electron blocking layer; 6-a light-emitting layer; 7-hole blocking/electron transporting layer; 8-electron injection layer; 9-cathode reflective electrode layer.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the accompanying drawings, which are provided for illustration only and are not intended to limit the scope of the invention.
In the following examples and comparative examples, the reagents, materials and instruments used were all commercially available as conventional reagents, conventional materials and conventional instruments unless otherwise specified, and the reagents involved therein were also synthesized by a conventional synthesis method.
Specific preparation examples of intermediates are described below by way of example 1, and the nomenclature of the intermediates of each example can be distinguished by arabic numerals, such as intermediate I1, intermediate I2, intermediate II1, intermediate II2, and the like.
EXAMPLE 1 preparation of the intermediate
EXAMPLE 1-1 preparation of intermediate I1
Figure BDA0001769358100000211
Step 1: introducing nitrogen into a 250mL three-neck flask, adding 0.05mol of raw material U1 and 0.06mol of Mg powder, dissolving with 60mL of dry tetrahydrofuran, and adding 0.0004mol of simple substance I2Heating to 40 deg.C, stirring until the solution turns from yellow to colorless, heating the above mixed solution to 80 deg.C, stirring and reacting for 4h, no magnesium powder remains, indicating reaction is complete, generating Grignard reagent intermediate V1,the next step is directly carried out without purification;
step 2: introducing nitrogen into a 250mL three-neck flask, adding 0.03mol of 9-fluorenone, dissolving with 40mL of dry tetrahydrofuran, slowly dropwise adding the intermediate V1 solution of the Grignard reagent, heating and refluxing for 15h to generate a large amount of white precipitate, cooling to room temperature, adding saturated NHCl4Converting the grignard salt to an alcohol; after the reaction is finished, extracting with diethyl ether, drying, rotary-steaming, passing through a silica gel column to obtain a yellowish solid tertiary alcohol intermediate W1 with HPLC purity of 98.8% and yield of 73.8%;
elemental analysis Structure (molecular formula C)25H18O): theoretical value C, 89.79; h, 5.43; o, 4.78; test values are: c, 89.78; h, 5.44; and O, 4.78. ESI-MS (M/z) (M)+): theoretical value is 334.14, found 334.21.
And step 3: adding 0.02mol of intermediate W1 into a 250mL three-necked bottle, dissolving the intermediate W1 with 50mL of toluene, slowly dropwise adding 48% HBr aqueous solution (40mL), stirring and reacting at 25 ℃ for 24 hours, separating liquid after the reaction is finished, extracting the aqueous phase with toluene, combining organic phases, drying with anhydrous sodium sulfate, filtering, washing a filter cake with ethyl acetate, and performing rotary evaporation on the filtrate and the washing liquid until no solvent exists, and passing through a silica gel column to obtain an intermediate I1 with the HPLC purity of 99.2% and the yield of 75.9%.
Elemental analysis Structure (molecular formula C)25H17Br): theoretical value C, 75.58; h, 4.31; br, 20.11; test values are: c, 75.57; h, 4.31; br, 20.12. ESI-MS (M/z) (M)+): theoretical value is 396.05, found 396.19.
The preparation method of the intermediate I1 comprises three steps: synthesizing an intermediate V from raw materials U and Mg powder; intermediate V and 9-fluorenone were synthesized as intermediate W, and then intermediate I was synthesized from intermediate W and 48% aqueous HBr. The preparation of other intermediate I is similar to that of intermediate I1, and the specific structure of intermediate I used in the present invention is shown in Table 1.
TABLE 1
Figure BDA0001769358100000212
Figure BDA0001769358100000221
EXAMPLE 1-2 preparation of intermediate II1
Figure BDA0001769358100000222
Step 1, adding 0.01mol of raw material A-1 and 0.015mol of raw material B-1 into a 250mL three-necked bottle under the protection of nitrogen, dissolving the raw materials with a mixed solvent of toluene and ethanol (wherein the mixed solvent is 90mL of toluene and 45mL of ethanol), and then adding 0.03mol of Na2CO3Aqueous solution (2M), stirred for 1h under nitrogen and then 0.0001mol Pd (PPh) was added3)4And heating and refluxing for 15h, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably evaporating the filtrate, and passing the residue through a silica gel column to obtain an intermediate S1-1; HPLC purity 98.5%, yield 78.5%;
elemental analysis Structure (molecular formula C)18H11NO3): theoretical value C, 74.73; h, 3.83; n, 4.84; o, 16.59; test values are: c, 74.75; h, 3.82; n, 4.84; and O, 16.58. ESI-MS (M/z) (M)+): theoretical value is 289.07, found 289.21.
Step 2: adding 0.02mol of intermediate S1-1 into a 250mL three-necked bottle under the protection of nitrogen, dissolving with 100mL of o-dichlorobenzene, adding 0.03mol of triphenylphosphine, stirring at 170-190 ℃ for reaction for 12-16 h, cooling to room temperature after the reaction is finished, filtering, decompressing and rotary-steaming the filtrate, and passing through a neutral silica gel column to obtain an intermediate S2-1; HPLC purity 97.2%, yield 77.8%;
elemental analysis Structure (molecular formula C)18H11NO): theoretical value C, 84.03; h, 4.31; n, 5.44; o, 6.22; test values are: c, 84.04; h, 4.31; n, 5.43; and O, 6.22. ESI-MS (M/z) (M)+): theoretical value is 257.08, found 257.25.
And step 3: in a 250mL three-necked flask, 0.02mol of intermediate S2-1, 0.03mol of raw material C-1, 0.05mol of sodium tert-butoxide and 0.2mmol of Pd were added under nitrogen protection2(dba)30.2mmol of tritertineStirring and mixing butyl phosphine with 150mL of methylbenzene, heating to 110-120 ℃, carrying out reflux reaction for 12-24 hours, and sampling a sample point plate to show that no intermediate S2-1 remains and the reaction is complete; naturally cooling to room temperature, filtering, carrying out reduced pressure rotary distillation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain an intermediate S3-1; HPLC purity 98.1%, yield 76.4%;
elemental analysis Structure (molecular formula C)24H15NO): theoretical value C, 86.46; h, 4.54; n, 4.20; o, 4.80; test values are: c, 86.45; h, 4.53; n, 4.21; and O, 4.81. ESI-MS (M/z) (M)+): theoretical value is 333.12, found 333.05.
And 4, step 4: adding 0.02mol of intermediate S3-1 into a 250mL three-necked bottle under the protection of nitrogen, dissolving with 50mL of acetic acid, and cooling to 0 ℃ by using an ice salt bath; weighing 0.025mol of liquid bromine, dissolving in 50mL of glacial acetic acid, slowly dropwise adding into an acetic acid solution of the intermediate S3-1, stirring for 5 hours at room temperature, sampling a sample point plate, and indicating that no intermediate S3-1 remains and the reaction is complete; after the reaction is finished, adding alkali liquor into the reaction liquid for neutralization, extracting by using dichloromethane, layering, taking an organic phase for filtration, decompressing and rotary-steaming the filtrate until no fraction is produced, and passing through a silica gel column to obtain an intermediate S4-1; HPLC purity 98.1%, yield 76.4%;
elemental analysis Structure (molecular formula C)24H14BrNO): theoretical value C, 69.92; h, 3.42; br, 19.38; n, 3.40; o, 3.88; test values are: c, 69.93; h, 3.43; br, 19.37; n, 3.39; and O, 3.88. ESI-MS (M/z) (M)+): theoretical value is 411.03, found 411.16.
And 5: adding 0.02mol of intermediate S4-1 into a 250mL three-necked flask under the protection of nitrogen, dissolving with 40mL tetrahydrofuran, cooling to-78 ℃, then adding 15mL tetrahydrofuran solution of 1.6mol/L n-butyllithium into the reaction system, reacting for 3h at-78 ℃, then adding 0.024mol triisopropyl borate, reacting for 2h, then raising the temperature of the reaction system to 0 ℃, adding 50mL 2mol/L hydrochloric acid solution, stirring for 3h, completely reacting, adding diethyl ether for extraction, adding anhydrous magnesium sulfate into the extract, drying, rotary steaming, and recrystallizing with ethanol solvent to obtain intermediate II 1. HPLC purity 95.6%, yield 72.1%;
elemental analysis Structure (score)Sub-formula C24H16BrNO3): theoretical value C, 76.42; h, 4.28; br, 2.87; n, 3.71; o, 12.72; test values are: c, 76.41; h, 4.28; br, 2.88; n, 3.71; o, 12.72. ESI-MS (M/z) (M)+): theoretical value is 377.12, found 377.24.
The synthesis of the intermediate II1 comprises five steps: synthesizing an intermediate S1-1 from the raw material A-1 and the raw material B-1; the intermediate S1-1 undergoes a cyclization reaction to form an intermediate S2-1; synthesizing an intermediate S3-1 by the intermediate S2-1 and the raw material C-1; bromination of intermediate S3-1 results in intermediate S4-1; finally, intermediate II1 was synthesized from intermediate S4-1 and triisopropyl borate. The preparation of other intermediate II is similar to that of intermediate II1, and the specific structure of intermediate II used in the present invention is shown in Table 2.
TABLE 2
Figure BDA0001769358100000231
Figure BDA0001769358100000241
Figure BDA0001769358100000251
Example 2 preparation of fluorene-centered Compound
EXAMPLE 2-1 preparation of Compound 6
Figure BDA0001769358100000252
In a 250mL three-necked flask, nitrogen gas was introduced, and 0.01mol of intermediate I4 and 0.015mol of intermediate II1 were added, dissolved in a mixed solvent of toluene and ethanol (90 mL of toluene and 45mL of ethanol), followed by addition of 0.03mol of Na2CO3Aqueous solution (2M), stirred for 1h under nitrogen and then 0.0001mol Pd (PPh) was added3)4And heating and refluxing for 15h, sampling a sample point plate, and completely reacting.Naturally cooling, filtering, rotatably evaporating filtrate, and passing residue through a silica gel column to obtain the target product with the purity of 97.8 percent and the yield of 73.5 percent. Elemental analysis Structure (molecular formula C)43H27NO): theoretical value C, 90.03; h, 4.74; n, 2.44; o, 2.79; test values are: c, 90.04; h, 4.73; n, 2.44; o, 2.79. ESI-MS (M/z) (M)+): theoretical value is 573.21, found 573.33.
EXAMPLE 2-2 preparation of Compound 18
Figure BDA0001769358100000253
Compound 18 was prepared as in example 2-1, except that intermediate II2 was used in place of intermediate II 1. Elemental analysis Structure (molecular formula C)49H31NO): theoretical value C, 90.57; h, 4.81; n, 2.16; o, 2.46; test value C, 90.58; h, 4.80; n, 2.16; o, 2.46. ESI-MS (M/z) (M)+): theoretical value is 649.24, found 649.35.
EXAMPLES 2-3 preparation of Compound 27
Figure BDA0001769358100000261
Compound 27 was prepared as in example 2-1, except that intermediate II3 was used in place of intermediate II 1. Elemental analysis Structure (molecular formula C)49H31NO): theoretical value C, 90.57; h, 4.81; n, 2.16; o, 2.46; test value C, 90.57; h, 4.81; n, 2.16; o, 2.46. ESI-MS (M/z) (M)+): theoretical value is 649.24, found 649.17.
EXAMPLES 2-4 preparation of Compound 30
Figure BDA0001769358100000262
Compound 30 was prepared as in example 2-1, except that intermediate II4 was used in place of intermediate II 1. Elemental analysis Structure (molecular formula C)49H31NO): theory of thingsTheoretical value C, 90.57; h, 4.81; n, 2.16; o, 2.46; test value C, 90.56; h, 4.81; n, 2.16; o, 2.47. ESI-MS (M/z) (M)+): theoretical value is 649.24, found 649.33.
EXAMPLES 2-5 preparation of Compound 39
：
Figure BDA0001769358100000263
Compound 39 was prepared as in example 2-1, except that intermediate II5 was used in place of intermediate II 1. Elemental analysis Structure (molecular formula C)49H29NO2): theoretical value C, 88.67; h, 4.40; n, 2.11; o, 4.82; test value C, 88.68; h, 4.40; n, 2.10; and O, 4.82. ESI-MS (M/z) (M)+): theoretical value is 663.22, found 663.35.
EXAMPLES 2-6 preparation of Compound 55
Figure BDA0001769358100000264
Compound 55 was prepared as in example 2-1, except intermediate II6 was used in place of intermediate II 1. Elemental analysis Structure (molecular formula C)49H29NS2): theoretical value C, 84.57; h, 4.20; n, 2.01; s, 9.21; test value C, 84.57; h, 4.20; n, 2.01; s, 9.21. ESI-MS (M/z) (M)+): theoretical value is 695.17, found 695.22.
EXAMPLES 2-7 preparation of Compound 72
Figure BDA0001769358100000271
Compound 72 was prepared as in example 2-1, except that intermediate II7 was used in place of intermediate II 1. Elemental analysis Structure (molecular formula C)52H35NS): theoretical value C, 88.48; h, 5.00; n, 1.98; s, 4.54; test value C, 88.49; h, 5.00; n, 1.98; and S, 4.53. ESI-MS (M/z) (M)+): theory of the inventionThe value was 705.25, found 705.36.
EXAMPLES 2-8 preparation of Compound 80
Figure BDA0001769358100000272
Compound 80 was prepared as in example 2-1, except that intermediate II8 was used in place of intermediate II 1. Elemental analysis Structure (molecular formula C)55H34N2S): theoretical value C, 87.50; h, 4.54; n, 3.71; s, 4.25; test value C, 87.51; h, 4.54; n, 3.71; and S, 4.24. ESI-MS (M/z) (M)+): theoretical value is 754.24, found 754.31.
EXAMPLES 2-9 preparation of Compound 90
Figure BDA0001769358100000273
Compound 90 was prepared as in example 2-1, except that intermediate II9 was used in place of intermediate II 1. Elemental analysis Structure (molecular formula C)49H31NO): theoretical value C, 90.57; h, 4.81; n, 2.16; o, 2.46; test value C, 90.57; h, 4.80; n, 2.17; o, 2.46. ESI-MS (M/z) (M)+): theoretical value is 649.24, found 649.18.
EXAMPLES 2-10 preparation of Compound 104
Figure BDA0001769358100000274
Compound 104 was prepared as in example 2-1, except that intermediate II10 was used in place of intermediate II 1. Elemental analysis Structure (molecular formula C)49H29NOS): theoretical value C, 86.57; h, 4.30; n, 2.06; o, 2.35; s, 4.72; test value C, 86.56; h, 4.30; n, 2.07; o, 2.35; and S, 4.72. ESI-MS (M/z) (M)+): theoretical value is 679.20, found 679.33.
EXAMPLES 2-11 preparation of Compound 111
Figure BDA0001769358100000281
Compound 111 was prepared as in example 2-1, except intermediate II11 was used in place of intermediate II1 and intermediate I1 was used in place of intermediate I4. Elemental analysis Structure (molecular formula C)49H31NO): theoretical value C, 90.57; h, 4.81; n, 2.16; o, 2.46; test value C, 90.56; h, 4.82; n, 2.16; o, 2.46. ESI-MS (M/z) (M)+): theoretical value is 649.24, found 649.31.
EXAMPLES 2-12 preparation of Compound 121
Figure BDA0001769358100000282
Compound 121 was prepared as in example 2-1, except intermediate II12 was used in place of intermediate II1 and intermediate I2 was used in place of intermediate I4. Elemental analysis Structure (molecular formula C)49H31NO): theoretical value C, 90.57; h, 4.81; n, 2.16; o, 2.46; test value C, 90.57; h, 4.82; n, 2.15; o, 2.46. ESI-MS (M/z) (M)+): theoretical value is 649.24, found 649.17.
EXAMPLES 2-13 preparation of Compound 136
Figure BDA0001769358100000283
Compound 136 was prepared as in example 2-1, except intermediate II13 was used in place of intermediate II 1. Elemental analysis Structure (molecular formula C)47H29NO): theoretical value C, 90.50; h, 4.69; n, 2.25; o, 2.56; test value C, 90.49; h, 4.70; n, 2.25; o, 2.56. ESI-MS (M/z) (M)+): theoretical value is 623.22, found 623.34.
EXAMPLES 2-14 preparation of Compound 158
Figure BDA0001769358100000284
Compound 158 was prepared as in example 2-1, except intermediate II14 was used in place of intermediate II1 and intermediate I3 was used in place of intermediate I4. Elemental analysis Structure (molecular formula C)47H29NO): theoretical value C, 90.50; h, 4.69; n, 2.25; o, 2.56; test value C, 90.51; h, 4.69; n, 2.24; o, 2.56. ESI-MS (M/z) (M)+): theoretical value is 623.22, found 623.27.
EXAMPLES 2-15 preparation of Compound 184
Figure BDA0001769358100000285
Compound 184 was prepared as in example 2-1, except intermediate II15 was used in place of intermediate II 1. Elemental analysis Structure (molecular formula C)55H35NO): theoretical value C, 91.01; h, 4.86; n, 1.93; o, 2.20; test value C, 91.00; h, 4.87; n, 1.93; o, 2.20. ESI-MS (M/z) (M)+): theoretical value is 725.27, found 725.34.
EXAMPLES 2-16 preparation of Compound 198
Figure BDA0001769358100000291
Compound 198 was prepared as in example 2-1, except intermediate II16 was used in place of intermediate II 1. Elemental analysis Structure (molecular formula C)49H29NO2): theoretical value C, 88.67; h, 4.40; n, 2.11; o, 4.82; test value C, 88.68; h, 4.40; n, 2.11; and O, 4.81. ESI-MS (M/z) (M)+): theoretical value is 663.22, found 663.29.
EXAMPLES 2-17 preparation of Compound 214
Figure BDA0001769358100000292
Compound 214 was prepared as in example 2-1, except that intermediate II17 was used instead of intermediate II 1. Elemental analysis Structure (molecular formula C)49H31NS): theoretical value C, 88.39; h, 4.69; n, 2.10; s, 4.81; test value C, 88.39; h, 4.69; n, 2.10; and S, 4.81. ESI-MS (M/z) (M)+): theoretical value is 665.22, found 665.34.
The organic compound of the present invention is used in a light-emitting device, and can be used as an electron blocking layer material or a light-emitting layer host material. The triplet level, HOMO level, cyclic voltammetric stability of the compounds of the invention were tested as shown in table 3.
TABLE 3
Figure BDA0001769358100000293
Figure BDA0001769358100000301
Note: the triplet energy level T1 was measured by Hitachi F4600 fluorescence spectrometer under the conditions of 2X 10-5A toluene solution of (4); the highest occupied molecular orbital HOMO energy level was tested by the ionization energy testing system (IPS3) in an atmospheric environment. The cyclic voltammetry stability is characterized by observing the redox characteristics of the material by cyclic voltammetry; and (3) testing conditions are as follows: the test sample was dissolved in a mixed solvent of dichloromethane and acetonitrile at a volume ratio of 2:1 at a concentration of 1mg/mL, and the electrolyte was 0.1M of an organic solution of tetrabutylammonium tetrafluoroborate or hexafluorophosphate. The reference electrode is an Ag/Ag + electrode, the counter electrode is a titanium plate, the working electrode is an ITO electrode, and the cycle time is 50 times.
The data in the table show that the organic compound has different HOMO energy levels and can be applied to different functional layers, and the compound has higher triplet state energy level, higher thermal stability and chemical stability, so that the efficiency and the service life of the manufactured OLED device containing the organic compound are improved.
The effect of the compound of the present invention in the application of the OLED device will be described in detail by example 3. In each example and comparative example included in example 3, the device fabrication process was completely the same, and the same substrate material and electrode material were used, and the film thickness of the electrode material was also kept consistent, except that the hole transport/electron blocking layer material in the device was changed, and the performance test results of each device are shown in tables 4 and 5.
Example 3 preparation of OLED device
Example 3-1 preparation of device 1
As shown in fig. 1, an electroluminescent device is prepared by the following steps:
a) cleaning the ITO anode layer 2 on the transparent substrate layer 1, respectively ultrasonically cleaning the ITO anode layer 2 with deionized water, acetone and ethanol for 15 minutes, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes;
b) evaporating HAT-CN as a hole injection layer 3 on the ITO anode layer 2 in a vacuum evaporation mode, wherein the evaporation thickness is 10 nm;
c) evaporating NPB as a hole transport layer 4 on the hole injection layer 3 in a vacuum evaporation mode, wherein the evaporation thickness is 60 nm;
d) evaporating the compound 6 of the invention as a hole transport/electron blocking layer 5 on the hole transport layer 4 in a vacuum evaporation mode, wherein the evaporation thickness is 20 nm;
e) a luminescent layer 6 is evaporated on the hole transport/electron barrier layer 5, the main material of the luminescent layer 6 is GHN, the doping material is Ir (ppy)3GHN and Ir (ppy)3The mass ratio of (1) to (9) and the thickness of 30 nm;
f) evaporating TPBI as a hole blocking/electron transport layer 7 on the luminescent layer 6 in a vacuum evaporation mode, wherein the evaporation thickness is 40 nm;
g) vacuum evaporation of an electron injection layer LiF serving as an electron injection layer 8 is carried out on the hole blocking/electron transport layer 7, and the evaporation thickness is 1 nm;
h) on the electron injection layer 8, a cathode Al was vacuum-deposited as a cathode reflective electrode layer 9, and the thickness was 100nm, thereby obtaining a device 1.
The structural formula of the material used in example 3 is as follows: after the electroluminescent device was fabricated according to the above procedure, IVL data and light decay life of the device were measured, and the results are shown in table 3.
Figure BDA0001769358100000311
Examples 3-2 preparation of devices 2-17 and comparative devices
The devices 2 to 17 and the comparative device were prepared in the same manner as in the device 1, and the same substrate material and electrode material were used, and the film thickness of the electrode material was kept the same, except that the material used for the hole transporting/electron blocking layer was different, and the specific data are shown in table 4.
TABLE 4
Figure BDA0001769358100000312
Figure BDA0001769358100000321
After the electroluminescent device was prepared, the device was measured at 10mA/cm2The current efficiency and lifetime at current density are shown in table 5.
TABLE 5
Figure BDA0001769358100000322
From the results in table 4, it can be seen that the fluorene-based compound prepared by the present invention can be applied to the fabrication of OLED light emitting devices, and compared with the comparative device examples, the efficiency and lifetime of the OLED material are greatly improved compared with the known OLED material, and especially the lifetime decay of the device is greatly improved.
In order to compare the efficiency attenuation conditions of different devices under high current density, the efficiency attenuation coefficient phi of each device is defined, wherein phi represents that the driving current is 100mA/cm2Maximum efficiency mu of time device100And deviceMaximum efficiency ofmDifference between the maximum efficiency mu and the100The larger the value of phi is, the more serious the efficiency roll-off of the device is, otherwise, the problem of rapid attenuation of the device under high current density is controlled. The efficiency attenuation coefficient φ of the devices 1-17 and the comparative device examples was determined and the results are shown in Table 6:
TABLE 6
Figure BDA0001769358100000323
Figure BDA0001769358100000331
As can be seen from the data in table 6, the organic light emitting device prepared by using the compound of the present invention has a smaller efficiency roll-off coefficient, which indicates that the organic electroluminescent device prepared by using the compound of the present invention can effectively reduce the efficiency roll-off.
The efficiency of the OLED device prepared by the compound is stable when the OLED device works at low temperature, the devices 1, 5 and 9 and the comparative device are subjected to efficiency test at the temperature of-10-80 ℃, and the obtained results are shown in Table 7 and figure 2.
TABLE 7
Figure BDA0001769358100000332
As can be seen from the data in table 7 and fig. 2, the devices 1, 5, and 9 are device structures in which the compound of the present invention and the known material are combined, and compared with the comparative device, the efficiency is high at low temperature, and the efficiency is steadily increased during the temperature increase.
In order to further test the beneficial effects of the compound of the present invention, the device 1 of the present invention and the device manufactured by the device comparative example were tested for reverse voltage leakage current, and the test results are shown in fig. 3. as can be seen from fig. 3, the device 1 using the compound of the present invention has a smaller leakage current and a more stable current curve than the device manufactured by the device comparative example, so that the compound of the present invention has a longer service life after being applied to the device manufacturing.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (2)

1. An organic electroluminescent device comprises an electron blocking layer, and is characterized in that the electron blocking layer is made of a material containing a compound shown as a structural general formula (1):
Figure FDA0003506817100000011
wherein L represents a single bond;
Ar2represented by phenyl, biphenyl, terphenyl or naphthyl;
in the general formula (1)
Figure FDA0003506817100000012
Expressed as:
Figure FDA0003506817100000013
Figure FDA0003506817100000014
Figure FDA0003506817100000015
any one of them.
2. The organic electroluminescent device according to claim 1, wherein the compound has a specific structural formula:
Figure FDA0003506817100000021
Figure FDA0003506817100000031
Figure FDA0003506817100000041
Figure FDA0003506817100000051
any one of them.
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