CN110885334A - Organic compound with benzo [1,2-b:3, 4-b' ] dibenzofuran as core and application thereof - Google Patents

Organic compound with benzo [1,2-b:3, 4-b' ] dibenzofuran as core and application thereof Download PDF

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CN110885334A
CN110885334A CN201811189237.3A CN201811189237A CN110885334A CN 110885334 A CN110885334 A CN 110885334A CN 201811189237 A CN201811189237 A CN 201811189237A CN 110885334 A CN110885334 A CN 110885334A
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陆颖
李崇
王芳
谢丹丹
张兆超
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Jiangsu Sunera Technology Co Ltd
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Abstract

The invention discloses a benzo [1,2-b:3, 4-b']The structure of the compound provided by the invention is shown as a general formula (1):
Figure DDA0001827045580000011
the compound of the invention is benzo [1,2-b:3, 4-b']Dibenzofuran is used as a core, has higher glass transition temperature and molecular thermal stability, appropriate HOMO and LUMO energy levels, higher triplet state energy level T1 and hole mobility, and can be used as a hole transport layer material or an electron blocking layer material of an organic electroluminescent device through device structure optimizationThe photoelectric property of the OLED device and the service life of the OLED device can be effectively improved by the layer material.

Description

Organic compound with benzo [1,2-b:3, 4-b' ] dibenzofuran as core and application thereof
Technical Field
The invention relates to the technical field of semiconductors, in particular to an organic compound taking benzo [1,2-b:3, 4-b' ] dibenzofuran as a core and application thereof.
Background
The organic electroluminescent 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 wide application prospect. The OLED light-emitting device is of a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and the various different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.
At present, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and will further expand to large-size application fields such as televisions, but compared with actual product application requirements, the light emitting efficiency, the service life, and other performances of the OLED device need to be further improved. The research on the improvement of the performance of the OLED light emitting device 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 OLED photoelectric functional material are needed 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 broad categories from the application, i.e., charge injection transport materials and light emitting materials, and further, the charge injection transport materials can be further divided into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials, and the light emitting materials can be further divided into main light emitting materials and doping materials.
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, and as a host material of a light-emitting layer, a material having good bipolar property, appropriate HOMO/LUMO energy level, etc. is required.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, and the OLED device structure applied in industry comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport 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 transport material, a light emitting material, an electron transport 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 materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different.
Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high 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 illumination industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and the development of organic functional materials with higher performance is very important as a material enterprise.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides an organic compound with benzo [1,2-b:3, 4-b' ] dibenzofuran as core and its application in organic electroluminescent devices. The organic compound provided by the invention has good thermal stability, higher glass transition temperature and proper HOMO, and the device adopting the organic compound provided by the invention can effectively improve the photoelectric property of an OLED device and the service life of the OLED device through structure optimization, thereby better adapting to and meeting the application requirements of panel manufacturing enterprises.
The specific technical scheme is as follows: a compound with benzo [1,2-b:3, 4-b' ] dibenzofuran as core, the structure of the compound is shown as general formula (1):
Figure BDA0001827045560000021
a, B, C in the general formula (1) are independently represented by a hydrogen atom or C1-10Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-30 membered heteroaryl containing one or more heteroatoms, or a structure of formula (2), and one and only one of A and B is a structure of formula (2);
Figure BDA0001827045560000022
wherein, L, L1、L2Is a single bond, substituted or unsubstituted C6-30Arylene, substituted or unsubstituted 5-30 membered heteroarylene containing one or more heteroatoms;
R1、R2each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted phenylpyridyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted terphenyl group, C6-30Aryl or 5-30 membered heteroaryl substituted amino, a structure represented by general formula (3) or general formula (4), and R1、R2Not simultaneously represented as phenyl;
Figure BDA0001827045560000031
in the general formulae (3) and (4), X1、X2、X3Independently represent-O-, -S-, -C (R)3)(R4) -or-N (R)5)-；X2、X3May also represent a single bond;
Z1each occurrence, identically or differently, being denoted C (R)6) Or N;
a neutralizing group L in the general formula (3)1Or L2Bonded Z1Represented as a carbon atom;
the R is3～R5Are 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; r3And R4Can also be connected with each other to form a ring;
the R is6Is hydrogen atom, fluorine atom, cyano group, C1-20Alkyl of (C)1-20Alkenyl 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 R6Can be bonded to each other to form a ring;
the substituent of the substitutable group is selected from cyano, halogen and C1-20Alkyl of (C)6-30One or more of aryl and 5-30-membered heteroaryl containing one or more heteroatoms;
the hetero atom in the heteroaryl is any one or more selected from oxygen atom, sulfur atom or nitrogen atom.
As a further improvement of the invention, the general formula (1) is represented by a structure represented by a general formula (II), a general formula (III) or a general formula (IV):
Figure BDA0001827045560000032
as a further improvement of the present invention, in said general formula (1), L, L1、L2Is shown as
Figure BDA0001827045560000033
Figure BDA0001827045560000034
Figure BDA0001827045560000041
(L-39) a structure represented by the following formula;
wherein Z represents N or C (R)7)，R7Each occurrence being the same or different and being represented by hydrogen atom, cyano group, fluorine atom, C1-20Alkyl radical, C6-20One of aryl or 5-20 membered heteroaryl containing one or more heteroatoms, and at least one R7Is not a hydrogen atom; two or more adjacent R7Can be bonded to each other to form a ring;
z at the bond to other groups is represented as a carbon atom.
As a further improvement of the present invention, in said general formula (1), L, L1、L2Is shown as
Single bond
Figure BDA0001827045560000042
Figure BDA0001827045560000043
Figure BDA0001827045560000051
The structure shown.
As a further improvement of the present invention, in the general formula (1), R1、R2Each independently is represented by:
Figure BDA0001827045560000052
Figure BDA0001827045560000061
(A-56) any one of the structures shown in (A-56);
wherein Z, which is identical or different at each occurrence, is represented by N or C (R)7)，R7Each occurrence being the same or different and being represented by hydrogen atom, cyano group, fluorine atom, C1-20Alkyl radical, C6-20One of aryl or 5-20 membered heteroaryl containing one or more heteroatoms, and at least one R7Is not a hydrogen atom; two or more adjacent R7Can be bonded to each other to form a ring;
and L1Or L2Z at the bonding site is represented as a carbon atom.
As a further improvement of the present invention, in the general formula (1), R1、R2Each independently is represented by:
Figure BDA0001827045560000062
Figure BDA0001827045560000063
any of the structures shown.
As a further improvement of the present invention, one of said A, B represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a biphenyl group, a naphthyl group, a naphthyridinyl group or a pyridyl group;
the R is3～R5Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, biphenyl, naphthyl, naphthyridinyl or pyridyl;
the R is6、R7Each independently represents 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 substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyridine group, a substituted or unsubstituted furyl group, a substituted or unsubstituted dibenzofuryl group, or a substituted or unsubstituted carbazolyl group;
the substituent of the substitutable group is one or more of fluorine atom, cyano, methyl, ethyl, propyl, isopropyl, tert-butyl, amyl, phenyl, naphthyl, biphenyl, naphthyridinyl, furyl, dibenzofuryl, carbazolyl or pyridyl.
As a further improvement of the invention, the compound has a specific structure as follows:
Figure BDA0001827045560000071
Figure BDA0001827045560000081
Figure BDA0001827045560000091
Figure BDA0001827045560000101
Figure BDA0001827045560000111
Figure BDA0001827045560000121
Figure BDA0001827045560000131
Figure BDA0001827045560000141
Figure BDA0001827045560000151
Figure BDA0001827045560000161
Figure BDA0001827045560000171
Figure BDA0001827045560000181
Figure BDA0001827045560000191
Figure BDA0001827045560000201
Figure BDA0001827045560000211
Figure BDA0001827045560000221
Figure BDA0001827045560000231
Figure BDA0001827045560000241
Figure BDA0001827045560000251
Figure BDA0001827045560000261
Figure BDA0001827045560000271
Figure BDA0001827045560000281
Figure BDA0001827045560000291
Figure BDA0001827045560000301
Figure BDA0001827045560000311
Figure BDA0001827045560000321
Figure BDA0001827045560000331
Figure BDA0001827045560000341
Figure BDA0001827045560000351
Figure BDA0001827045560000361
Figure BDA0001827045560000371
any one of them.
In a second aspect, the present invention provides the use of an organic compound containing benzo [1,2-b:3, 4-b' ] dibenzofuran as described above for the preparation of an organic electroluminescent device.
A third aspect of the present invention is to provide an organic electroluminescent device characterized in that the above organic electroluminescent device comprises at least one functional layer containing the above organic compound containing benzo [1,2-b:3, 4-b' ] dibenzofuran.
In a fourth aspect, the present invention provides an organic electroluminescent element comprising a hole transporting layer or an electron blocking layer, wherein the hole transporting layer or the electron blocking layer contains the organic compound containing benzo [1,2-b:3, 4-b' ] dibenzofuran.
A fifth aspect of the present invention is to provide a lighting or display element having such a feature, including the organic electroluminescent device described above.
The invention has the beneficial effects that:
the compound takes benzo [1,2-b:3, 4-b' ] dibenzofuran as a mother nucleus and is connected with a diarylamino branched chain compound, the compound has higher thermal stability, strong hole transport capacity and high hole mobility, can be used as a hole transport layer material, and the high hole transport rate can improve the efficiency of an organic electroluminescent device; under a proper LUMO energy level, the organic electroluminescent device also plays a role in blocking electrons, improves the recombination efficiency of excitons in a light-emitting layer, reduces the efficiency roll-off under high current density, reduces the voltage of the device, improves the current efficiency of the device and prolongs the service life of the device.
The compound takes benzo [1,2-b:3, 4-b' ] dibenzofuran as the center and diarylamino as the branch chain, and after the material is formed into a film, all the branch chains can be crossed with each other to form a high-compactness film layer, so that the leakage current of the material after the application of an OLED device is reduced, and the service life of the device is prolonged.
Compared with the compound 1 disclosed in patent JP2012028548A, the compound has higher hole mobility when the diarylamine is connected with benzo [1,2-b:3, 4-b' ] dibenzofuran; the molecular weight is moderate, the glass transition temperature and the decomposition temperature are higher, and the evaporation temperature is regulated and controlled by adding aryl or heteroaryl between a mother nucleus and a branched chain, so that the industrial window is wider; when the compound is applied to an OLED device, the structure of the device is optimized, so that high film stability can be kept, the photoelectric property of the OLED device can be effectively improved, and the service life of the OLED device can be effectively prolonged.
The compound provided by the invention has higher glass transition temperature and molecular thermal stability, appropriate 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.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention;
FIG. 2 is a graph of efficiency measured at different temperatures for a device made according to the present invention and a comparative device;
FIG. 3 is a graph of reverse voltage leakage current test curves for devices fabricated in example 7 of the device of the present invention and comparative example 1 of the device;
in the drawings: 1 is a transparent substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is hole transmission, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is an electron transmission or hole blocking layer, 8 is an electron injection layer, 9 is a cathode layer, and 10 is a CPL layer.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Synthesis of intermediate D
Figure BDA0001827045560000391
(1) Weighing a raw material E-1 and a raw material G, and dissolving the raw materials in a toluene-ethanol mixed solvent with a volume ratio of 1.5-3.0: 1; then adding Na2CO3Aqueous solution, Pd (PPh)3)4(ii) a Stirring the mixed solution at 90-110 ℃ for reaction for 10-24 hours under an inert atmosphere, cooling to room temperature, filtering the reaction solution, performing rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate H; the molar ratio of the raw material E-1 to the raw material G is 1: 1.5-3.0; the Pd (PPh)3)4The molar ratio of the raw material E-1 to the raw material E-1 is 0.006-0.02: 1; the Na is2CO3The molar ratio of the raw material E-1 to the raw material E-1 is 2.0-3.0: 1; the dosage of the toluene-ethanol mixed solvent is 0.01mol, 30-40ml of toluene and 15-20ml of ethanol are added into the raw material E-1;
(2) weighing the intermediate H and p-toluenesulfonic acid under the protection of nitrogen, dissolving with toluene, heating to 90-110 ℃, and reacting for 10-24 hours; sampling a spot plate, and showing that no intermediate H remains and the reaction is complete; after the reaction is finished, adding a saturated sodium carbonate solution into the reaction system for quenching, extracting with ethyl acetate, separating liquid, drying an organic phase with anhydrous sodium sulfate, decompressing, carrying out rotary evaporation until no fraction is produced, and passing the obtained crude product through a neutral silica gel column to obtain an intermediate D; the molar ratio of the intermediate H to the p-toluenesulfonic acid is 1: 1-1.5; 30-40ml of toluene is added into the intermediate H with the dosage of the toluene being 0.01 mol; adding 5-15ml of saturated sodium carbonate solution into the intermediate H with the dosage of the saturated sodium carbonate solution being 0.01 mol; adding 30-45ml of ethyl acetate into the intermediate H with the dosage of the ethyl acetate being 0.01mol, and adding the ethyl acetate into the intermediate H in three times;
this is exemplified by the synthesis of intermediate D-1:
Figure BDA0001827045560000401
(1) a500 mL three-necked flask was charged with 0.05mol of E-1 as a starting material and 0.1mol of G-1 as a starting material under nitrogen protection, dissolved in a mixed solvent (180mL of toluene and 90mL of ethanol), and then charged with a solution containing 0.15mol of Na2CO3Na of (2)2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0005mol Pd (PPh) was added3)4After heating for 15 hours, the reaction was completed by sampling the sample plate. Naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain an intermediate H-1 with the HPLC purity of 99.3 percent and the yield of 61.5 percent.
Elemental analysis Structure (molecular formula C)18H11BrO3): theoretical value C, 60.87; h, 3.12; br, 22.50; test values are: c, 60.84; h, 3.13; br, 22.51. ESI-MS (M/z) (M +): theoretical value is 353.99, found 354.18.
(2) Adding 0.03mol of intermediate H-1 and 0.036mol of p-toluenesulfonic acid into a 250mL three-neck flask under the protection of nitrogen, dissolving the mixture by using 100mL of toluene, heating to 100 ℃, and reacting for 15 hours; sampling a spot plate, and showing that no intermediate H-1 remains and the reaction is complete; after the reaction, 30ml of saturated sodium carbonate solution was added to the reaction system to quench, and the mixture was extracted with (30ml x 3) ethyl acetate, separated, the organic phase was dried over anhydrous sodium sulfate and then rotary evaporated under reduced pressure until no fraction was obtained, and the obtained crude product was passed through a neutral silica gel column to obtain intermediate D-1 with HPLC purity of 99.2% and yield of 55.4%.
Elemental analysis Structure (molecular formula C)18H9BrO2): theoretical value C, 64.12; h, 2.69; br, 23.70; test values are: c, 64.11; h, 2.68; br, 23.71. ESI-MS (M/z) (M +): theoretical value is 335.98, found 336.20.
Synthesizing an intermediate D according to a preparation method of the intermediate D-1, wherein the synthesis of the intermediate D comprises two steps: the raw material E and the raw material G react through Suzuki to generate an intermediate H; the intermediate H undergoes a cyclization reaction to generate an intermediate D, and the specific structure is shown in Table 1.
TABLE 1
Figure BDA0001827045560000402
Figure BDA0001827045560000411
The synthesis of starting material B-13 was carried out according to the method reported in the reference (Palladium-catalyzed Selective amines of aryl (haloaryl) amines with 9H-Carbazole Derivatives; DOI:10.1002/adsc.201701356) as follows:
Figure BDA0001827045560000421
(1) under nitrogen atmosphere, a 500ml three-neck flask was charged with 0.01mol of p-dibromobenzene, 0.011mol of carbazole, 0.03mol of sodium tert-butoxide, 5X 10-5mol Pd2(dba)3And 5X 10-5After the reaction was completed, 150ml of toluene was added to dissolve tri-t-butylphosphine, and the mixture was heated to 110 ℃ and refluxed for 15 hours, and the reaction was observed by TLC until the reaction was completed. Nature of natureCooling to room temperature, filtering, and rotatably evaporating the filtrate until no fraction is obtained. The resulting material was purified by silica gel column (petroleum ether as eluent) to give the target intermediate Z1The yield thereof was found to be 76.9%.
(2) 0.01mol of intermediate Z was added to a 500ml three-necked flask under a nitrogen atmosphere10.011mol of 4-amino-p-terphenyl, 0.03mol of sodium tert-butoxide and 5 x 10 mol of sodium tert-butoxide-5mol Pd2(dba)3And 5X 10-5After the reaction was completed, 150ml of toluene was added to dissolve tri-t-butylphosphine, and the mixture was heated to 110 ℃ and refluxed for 15 hours, and the reaction was observed by TLC until the reaction was completed. Naturally cooling to room temperature, filtering, and rotatably evaporating the filtrate until no fraction is obtained. The resulting material was purified by silica gel column (petroleum ether as eluent) to give the desired product in 99.7% purity and 73.4% yield.
Elemental analysis Structure (molecular formula C)36H26N2): theoretical value: c, 88.86; h, 5.39; n, 5.76; test values are: c, 88.87; h, 5.41; n, 5.78. ESI-MS (M/z) (M +): theoretical value is 486.21, found 486.23.
Synthesis of raw Material B-14:
Figure BDA0001827045560000422
to a 500ml three-necked flask, 0.01mol of 4-bromo-4, -biphenyl-diphenylamine and 0.015mol of Z were added under a nitrogen atmosphere20.02mL of 1mol/mL aqueous sodium carbonate solution, 2X 10-5mol Pd(PPh3)4And then adding 150ml of a toluene ethanol mixed solvent with the volume ratio of 1.5-3.0: 1 for dissolving, heating to 110 ℃, refluxing for 24 hours, and observing the reaction by using TLC until the reaction is complete. Naturally cooling to room temperature, filtering, and rotatably evaporating the filtrate until no fraction is obtained. The resulting material was purified by silica gel column (petroleum ether as eluent) to give the desired product in 99.7% purity and 83.4% yield.
Elemental analysis Structure (molecular formula C)36H26N2): theoretical value: c, 88.86; h, 5.39; n, 5.76; test values are: c, 88.88; h, 5.42; n, 5.78. ESI-MS (M/z) (M +): theoretical value is 486.21, found 486.23.
The synthesis of the other a-series starting materials is analogous to the two preparation methods described above and can be obtained by both types of reactions described above.
Example 1: synthesis of Compound 1:
Figure BDA0001827045560000431
adding 0.01mol of raw material A-1, 0.012mol of intermediate D-5 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 5 multiplied by 10-5molPd2(dba)3，5×10-5mol P(t-Bu)3Heating 0.03mol of sodium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, and sampling a point plate to show that no bromide is left and the reaction is complete; naturally cooling to room temperature, filtering, rotatably evaporating the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain the target product, wherein the HPLC purity is 99.54%, and the yield is 73.4%. Elemental analysis Structure (molecular formula C)54H33NO3): theoretical value C, 87.19; h, 4.47; n, 1.88; test value C, 87.23; h, 4.46; n, 1.86. HPLC-MS: the molecular weight of the material is 743.25, and the measured molecular weight is 743.32.
Example 2: synthesis of compound 15:
Figure BDA0001827045560000432
compound 15 was prepared as in example 1, except that starting material B-2 was used in place of starting material B-1; elemental analysis Structure (molecular formula C)54H39NO2): theoretical value C, 88.38; h, 5.36; n, 1.91; test values are: c, 88.37; h, 5.41; n, 1.87. HPLC-MS: theoretical value is 733.30, found 733.68.
Example 3: synthesis of compound 30:
Figure BDA0001827045560000433
compound 30 was prepared as in example 1, except that the starting material B-3 was used instead of the starting materialB-1; elemental analysis Structure (molecular formula C)60H37NO3): theoretical value C, 87.89; h, 4.55; n, 1.71; test values are: c, 87.85; h, 4.58; n, 1.73. HPLC-MS: theoretical value is 819.28, found 819.51.
Example 4: synthesis of compound 71:
Figure BDA0001827045560000441
compound 71 is prepared as in example 1, except that starting material B-4 is substituted for starting material B-1 and intermediate D-6 is substituted for intermediate D-5; elemental analysis Structure (molecular formula C)60H37NO3): theoretical value C, 87.89; h, 4.55; n, 1.71; test values are: c, 87.83; h, 4.59; n, 1.68. HPLC-MS: theoretical value is 819.28, found 819.58.
Example 5: synthesis of compound 96:
Figure BDA0001827045560000442
compound 96 is prepared as in example 1, except that starting material B-1 is replaced with starting material B-5 and intermediate D-5 is replaced with intermediate D-6; elemental analysis Structure (molecular formula C)60H37NO3): theoretical value C, 87.89; h, 4.55; n, 1.71; test values are: c, 87.92; h, 4.54; n, 1.69. HPLC-MS: theoretical value is 819.28, found 819.61.
Example 6: synthesis of compound 135:
Figure BDA0001827045560000443
compound 135 can be prepared by the same method as in example 1, except that starting material B-4 is used instead of starting material B-1, and intermediate D-2 is used instead of intermediate D-5; elemental analysis Structure (molecular formula C)54H33NO3): theoretical value C, 87.19; h, 4.47; n, 1.88; test value C, 87.21; h, 4.48; n, 1.85. HPLC-MS: the molecular weight of the material is 743.25, and the measured molecular weight is 743.52.
Example 7: synthesis of compound 138:
Figure BDA0001827045560000451
compound 138 is prepared as in example 1, except that starting material B-6 is substituted for starting material B-1 and intermediate D-2 is substituted for intermediate D-5; elemental analysis Structure (molecular formula C)54H31NO4): theoretical value C, 85.58; h, 4.12; n, 1.85; test value C, 85.61; h, 4.11; n, 1.84. HPLC-MS: the molecular weight of the material is 757.23, and the measured molecular weight is 757.48.
Example 8: synthesis of compound 155:
Figure BDA0001827045560000452
compound 155 can be prepared by the same method as in example 1, except that starting material B-7 is used instead of starting material B-1, and intermediate D-2 is used instead of intermediate D-5; elemental analysis Structure (molecular formula C)63H41NO3): theoretical value of C, 87.99; h, 4.81; n, 1.63; test value C, 88.03; h, 4.78; n, 1.61. HPLC-MS: the molecular weight of the material is 859.31, and the measured molecular weight is 859.62.
Example 9: synthesis of compound 162:
Figure BDA0001827045560000453
compound 162 can be prepared as in example 1, except that starting material B-8 is substituted for starting material B-1 and intermediate D-2 is substituted for intermediate D-5; elemental analysis Structure (molecular formula C)54H33NO3): theoretical value C, 87.19; h, 4.47; n, 1.88; test value C, 87.22; h, 4.45; and N, 1.90. HPLC-MS: the molecular weight of the material is 743.25, and the measured molecular weight is 743.55.
Example 10: synthesis of compound 203:
Figure BDA0001827045560000461
compound 203 is prepared as in example 1, except that starting material B-9 is substituted for starting material B-1 and intermediate D-1 is substituted for intermediate D-5; elemental analysis Structure (molecular formula C)60H37NO3): theoretical value C, 87.89; h, 4.55; n, 1.71; test values are: c, 87.91; h, 4.57; n, 1.68. HPLC-MS: theoretical value is 819.28, found 819.48.
Example 11: synthesis of compound 220:
Figure BDA0001827045560000462
compound 220 is prepared as in example 1, except that intermediate A-10 is substituted for intermediate A-1 and intermediate D-1 is substituted for intermediate D-5; elemental analysis Structure (molecular formula C)57H37NO3): theoretical value C, 87.33; h, 4.76; n, 1.79; test values are: c, 87.37; h, 4.75; n, 1.76. HPLC-MS: theoretical value is 783.28, found 783.55.
Example 12: synthesis of compound 264:
Figure BDA0001827045560000463
compound 264 was prepared as in example 1, except that starting material B-11 was used instead of starting material B-1 and intermediate D-7 was used instead of intermediate D-5; elemental analysis Structure (molecular formula C)54H33NO3): theoretical value C, 87.19; h, 4.47; n, 1.88; test value C, 87.17; h, 4.46; and N, 1.91. HPLC-MS: the molecular weight of the material is 743.25, and the measured molecular weight is 743.38.
Example 13: synthesis of compound 283:
Figure BDA0001827045560000471
compound 283 is prepared as in example 1, except that starting material B-12 is substituted for starting material B-1 and intermediate D-8 is substituted for intermediate D-5; elemental analysis Structure (molecular formula C)54H33N2O3): theoretical value C, 85.47; h, 4.52; n, 3.69; test value C, 85.45; h, 4.51; and N, 3.68. HPLC-MS: the molecular weight of the material is 758.26, and the measured molecular weight is 758.25.
Example 14: synthesis of compound 303:
Figure BDA0001827045560000472
compound 303 is prepared as in example 1, except that starting material B-13 is substituted for starting material B-1 and intermediate D-4 is substituted for intermediate D-5; elemental analysis Structure (molecular formula C)54H34N2O2): theoretical value C, 87.31; h, 4.61; n, 3.77; test value C, 97.35; h, 4.58; and N, 3.76. HPLC-MS: the molecular weight of the material is 742.26, and the measured molecular weight is 742.47.
Example 15: synthesis of compound 316:
Figure BDA0001827045560000473
compound 316 can be prepared by the same procedure as in example 1, except that starting material B-14 is substituted for starting material B-1 and intermediate D-3 is substituted for intermediate D-5; elemental analysis Structure (molecular formula C)54H34N2O2): theoretical value C, 87.31; h, 4.61; n, 3.77; test value C, 97.32; h, 4.56; n, 3.79. HPLC-MS: the molecular weight of the material is 742.26, and the measured molecular weight is 742.61.
Example 15: synthesis of compound 332:
Figure BDA0001827045560000474
compound 332 is prepared as in example 1, except that starting material B-1 is replaced with starting material B-15 and intermediate D-5 is replaced with intermediate D-9; elemental analysis Structure (molecular formula C)45H31NO2): theoretical value C, 87.49; h, 5.06; n, 2.27; test value C, 87.55; h, 5.03; and N, 2.26. HPLC-MS: the molecular weight of the material is 617.24, and the measured molecular weight is 617.75.
The compound of the invention is used in a luminescent device, can be used as an electron blocking layer material, and can also be used as a hole transport layer material. The compounds prepared in the above examples of the present invention were tested for thermal performance, T1 energy level, and HOMO energy level, respectively, and the test results are shown in table 2:
TABLE 2
Figure BDA0001827045560000481
Note: the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the thermogravimetric temperature Td is a temperature at which 1% of the weight loss is observed in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and the nitrogen flow rate is 20 mL/min; 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 a photoelectron emission spectrometer (AC-2 type PESA) in an atmospheric environment.
The data in the table show that the organic compound has high glass transition temperature, can improve the phase stability of the material film, and further improves the service life of the device; the high T1 energy level can block the energy loss of the light-emitting layer, thereby improving the light-emitting efficiency of the device; the appropriate HOMO energy level can solve the problem of carrier injection and can reduce the voltage of the device. Therefore, after the organic compound taking benzo [1,2-b:3, 4-b' ] dibenzofuran as the core is used for different functional layers of an OLED device, the luminous efficiency and the service life of the device can be effectively improved.
The effect of the use of the synthesized materials of the present invention in OLED devices is detailed below by device examples 1-17 and comparative example 1. Compared with the device embodiment 1, the device embodiments 2 to 17 and the device comparative example 1 of the present invention have the same device manufacturing process, and adopt the same substrate material and electrode material, and the film thickness of the electrode material is also kept consistent, except that the hole transport layer material or the electron blocking layer material in the device is replaced. The results of the performance tests of the devices obtained in the examples are shown in table 4.
Device example 1
Transparent substrate layer/ITO anode layer/hole injection layer (HAT-CN, thickness 10 nm)/hole transport layer (HT-1, thickness 60 nm)/electron blocking layer (Compound 3, thickness 20 nm)/light emitting layer (GH1, GH2 and GD-1) were co-doped in a weight ratio of 45:45:10, thickness 40 nm)/hole blocking/electron transport layer (ET-1 and Liq, co-doped in a weight ratio of 1:1, thickness 40 nm)/electron injection layer (LiF, thickness 1 nm)/cathode layer (Mg and Ag, co-doped in a weight ratio of 9:1, thickness 15nm)/CPL layer (Compound CP-1, thickness 70 nm).
The preparation process comprises the following steps:
as shown in fig. 1, the transparent substrate layer 1 is a transparent substrate, such as a transparent PI film, glass, or the like. The ITO anode layer 2 (having a film thickness of 150nm) was washed by alkali washing, pure water washing, drying, and then ultraviolet-ozone washing to remove organic residues on the surface of the transparent ITO. On the ITO anode layer 2 after the above washing, HAT-CN having a film thickness of 10nm was deposited by a vacuum deposition apparatus to be used as the hole injection layer 3. Then, HT-1 was evaporated to a thickness of 60nm as a hole transport layer. Compound 1 was then evaporated to a thickness of 20nm as an electron blocking layer. After the evaporation of the hole transport material is finished, the light emitting layer 6 of the OLED light emitting device is manufactured, and the structure of the light emitting layer 6 comprises GH1 and GH2 used by the OLED light emitting layer 6 as main materials, GD-1 used as a doping material, the doping proportion of the doping material is 10% by weight, and the thickness of the light emitting layer is 40 nm. After the light-emitting layer 6, the electron transport layer materials ET-1 and Liq are continuously vacuum-evaporated. The vacuum evaporation film thickness of the material was 40nm, and this layer was a hole-blocking/electron-transporting layer 7. On the hole-blocking/electron-transporting layer 7, a lithium fluoride (LiF) layer having a film thickness of 1nm was formed by a vacuum evaporation apparatus, and this layer was an electron-injecting layer 8. On the electron injection layer 8, a vacuum deposition apparatus was used to produce a 15 nm-thick Mg: an Ag electrode layer, which is used as the cathode layer 9. On the cathode layer 9, 70nm of CP-1 was vacuum-deposited as a CPL layer 10. After the OLED light emitting device was completed as described above, the anode and the cathode were connected by a known driving circuit, and the current efficiency of the device and the lifetime of the device were measured, and after the fabrication of the electroluminescent device was completed according to the above-described steps, the driving voltage and the current efficiency of the device were measured, and the results are shown in table 3. The molecular structural formula of the related existing materials is shown as follows:
Figure BDA0001827045560000501
TABLE 3
Figure BDA0001827045560000502
Figure BDA0001827045560000511
Note: comparative example of representative device
The inspection data of the obtained electroluminescent device are shown in Table 4.
TABLE 4
Figure BDA0001827045560000521
From the results in table 4, it can be seen that the organic compound of the present invention can be applied to the fabrication of OLED light emitting devices, and compared with the comparative examples, the efficiency and lifetime of the organic compound are greatly improved compared with those of the known OLED materials, especially the lifetime of the organic compound is greatly prolonged.
Further, the efficiency of the OLED device prepared by the material is stable when the OLED device works at low temperature, the efficiency tests are carried out on the device examples 3, 7 and 16 and the device comparative example 1 at the temperature of-10-80 ℃, and the obtained results are shown in the table 5 and the figure 2.
TABLE 5
Figure BDA0001827045560000522
As can be seen from the data in table 5 and fig. 2, device examples 3, 7 and 16 are device structures in which the material of the present invention and the known material are combined, and compared with device comparative example 1, the efficiency is high at low temperature, and the efficiency is smoothly increased in the temperature increasing process.
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 (10)

1. A compound with benzo [1,2-b:3, 4-b' ] dibenzofuran as a core, which is characterized in that the structure of the compound is shown as a general formula (1):
Figure FDA0001827045550000011
a, B, C in the general formula (1) are independently represented by a hydrogen atom or C1-10Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-30 membered heteroaryl containing one or more heteroatoms, or a structure of formula (2), and one and only one of A and B is a structure of formula (2);
Figure FDA0001827045550000012
in the general formula (2), L, L1、L2Is a single bond, substituted or unsubstituted C6-30Arylene, substituted or unsubstituted 5-30 membered heteroarylene containing one or more heteroatoms;
R1、R2each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted phenylpyridyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted terphenyl group, C6-30Aryl or 5-30 membered heteroaryl substituted amino, a structure represented by general formula (3) or general formula (4), and R1、R2Not simultaneously represented as phenyl;
Figure FDA0001827045550000013
in the general formulae (3) and (4), X1、X2、X3Independently represent-O-, -S-, -C (R)3)(R4) -or-N (R)5)-；X2、X3May also represent a single bond;
Z1each occurrence, identically or differently, being denoted C (R)6) Or N;
a neutralizing group L in the general formula (3)1Or L2Bonded Z1Represented as a carbon atom;
the R is3～R5Are 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; r3And R4Can also be connected with each other to form a ring;
the R is6Is hydrogen atom, fluorine atom, cyano group, C1-20Alkyl of (C)1-20Alkenyl 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 R6Can be bonded to each other to form a ring;
the substituent of the substitutable group is selected from cyano, halogen and C1-20Alkyl of (C)6-30One or more of aryl and 5-30-membered heteroaryl containing one or more heteroatoms;
the hetero atom in the heteroaryl is any one or more selected from oxygen atom, sulfur atom or nitrogen atom.
2. The compound of claim 1, wherein formula (1) is represented by formula (ii), formula (iii) or formula (IV):
Figure FDA0001827045550000021
3. the compound of claim 1, wherein in the formula (1), L, L1、L2Expressed as:
Figure FDA0001827045550000022
the structure shown.
4. The compound of claim 1, wherein in the formula (1), L, L1、L2Expressed as:
Figure FDA0001827045550000031
the structure shown;
wherein Z represents N or C (R)7)，R7Each occurrence being the same or different and being represented by hydrogen atom, cyano group, fluorine atom, C1-20Alkyl radical, C6-20One of aryl or 5-20 membered heteroaryl containing one or more heteroatoms, and at least one R7Is not a hydrogen atom; two or more adjacent R7Can be bonded to each other to form a ring;
z at the bonding site with other groups is represented as a carbon atom.
5. A benzo [1,2-b:3,4-b 'according to claim 4']A dibenzofuran-core compound represented by the general formula (1), wherein R is1、R2Each independently is represented by:
Figure FDA0001827045550000032
Figure FDA0001827045550000041
Figure FDA0001827045550000051
Figure FDA0001827045550000052
any one of (a);
wherein Z, which is identical or different at each occurrence, is represented by N or C (R)7)，R7Each occurrence being the same or different and being represented by hydrogen atom, cyano group, fluorine atom, C1-20Alkyl radical, C6-20One of aryl, 5-20 membered heteroaryl containing one or more heteroatoms, and at least one R7Is not a hydrogen atom; two or more adjacent R7Can be bonded to each other to form a ring;
and L1Or L2Z at the bonding site is represented as a carbon atom.
6. The benzo [1,2-b:3, 4-b' ] dibenzofuran-based compound of claim 4, wherein one of said A, B represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a biphenyl group, a naphthyl group, a naphthyridinyl group or a pyridyl group;
the R is3～R5Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, biphenyl, naphthyl, naphthyridinyl or pyridyl;
the R is6、R7Each independently represents 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 substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyridine group, a substituted or unsubstituted furyl group, a substituted or unsubstituted dibenzofuryl group, or a substituted or unsubstituted carbazolyl group;
the substituent of the substitutable group is one or more of fluorine atom, cyano, methyl, ethyl, propyl, isopropyl, tert-butyl, amyl, phenyl, naphthyl, biphenyl, naphthyridinyl, furyl, dibenzofuryl, carbazolyl or pyridyl.
7. The compound with benzo [1,2-b:3, 4-b' ] dibenzofuran as core according to claim 1, wherein the specific structure of the compound is as follows:
Figure FDA0001827045550000053
Figure FDA0001827045550000061
Figure FDA0001827045550000071
Figure FDA0001827045550000081
Figure FDA0001827045550000091
Figure FDA0001827045550000101
Figure FDA0001827045550000111
Figure FDA0001827045550000121
Figure FDA0001827045550000131
Figure FDA0001827045550000141
Figure FDA0001827045550000151
Figure FDA0001827045550000161
Figure FDA0001827045550000171
Figure FDA0001827045550000181
Figure FDA0001827045550000191
Figure FDA0001827045550000201
Figure FDA0001827045550000211
Figure FDA0001827045550000221
Figure FDA0001827045550000231
Figure FDA0001827045550000241
Figure FDA0001827045550000251
Figure FDA0001827045550000261
Figure FDA0001827045550000271
Figure FDA0001827045550000281
Figure FDA0001827045550000291
Figure FDA0001827045550000301
Figure FDA0001827045550000311
Figure FDA0001827045550000321
Figure FDA0001827045550000331
any one of them.
8. An organic electroluminescent element, characterized in that at least one functional layer contains a compound having benzo [1,2-b:3, 4-b' ] dibenzofuran as claimed in any one of claims 1 to 7 as a core.
9. The organic electroluminescent device according to claim 8, comprising an electron blocking layer or a hole transporting layer, wherein the electron blocking layer or the hole transporting layer contains the compound with benzo [1,2-b:3, 4-b' ] dibenzofuran as core according to any one of claims 1 to 9.
10. A lighting or display element comprising the organic electroluminescent device according to claims 8 to 9.
CN201811189237.3A 2018-09-11 2018-10-12 Organic compound with benzo [1,2-b:3, 4-b' ] dibenzofuran as core and application thereof Withdrawn CN110885334A (en)

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