CN114292287A - Polycyclic compound, preparation method thereof and organic electroluminescent device - Google Patents
Polycyclic compound, preparation method thereof and organic electroluminescent device Download PDFInfo
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Abstract
The invention relates to a polycyclic compound, a preparation method thereof and an organic electroluminescent device. The polycyclic compound takes a weak acceptor boron atom as a center, and the periphery is bonded with a large-volume rigid electron-donating group, carbazole, arylamine and the like, so that a D-A type molecular design from the periphery to the center is formed, and compared with a device prepared by polycyclic compound materials containing the same elements in the prior art, an organic electroluminescent device prepared by the polycyclic compound has obvious advantages in starting voltage, luminous efficiency, light color, service life and glass transition temperature, and is an ideal deep blue luminescent material.
Description
Technical Field
The invention relates to the field of photoelectric materials, in particular to a polycyclic compound, a preparation method thereof and an organic electroluminescent device.
Background
OLEDs, i.e., organic light emitting diodes, are also known as organic electroluminescent displays. The OLED has a self-luminous characteristic, adopts a very thin organic material coating layer and a glass substrate, emits light when current passes through the organic material coating layer, has a large viewing angle of an OLED display screen, and can significantly save electric energy, so the OLED is regarded as one of the most promising products in the 21 st century. However, to date, OLED devices have not achieved widespread use, where device efficiency is an important reason that limits their popularity.
Phosphorescent materials are the most efficient class of organic electroluminescent materials. However, from the perspective of device stability and cost, the phosphorescent material utilizes triplet excitons to emit light, has a long service life, is easy to generate exciton accumulation when the injection current is increased, and has reduced luminous efficiency, so that the stability of the device is greatly reduced; the fluorescent material is low in price because precious metal is not needed, and the chemical property is more stable, so that the manufacturing cost of the device is greatly reduced, and the fluorescent material is more valuable in the aspect of practical application.
The electron donating groups available in the design of the fluorescent material are fewer than the electron withdrawing groups, the electron donating groups available in the molecular design of the blue-light fluorescent material are fewer, and the electron donating groups are commonly used as groups such as five-membered carbazole, six-membered acridine and the like, but the stability of the acridine group is inferior to that of the carbazole group, so that the problems of low efficiency, short service life, impure light color and the like of the current blue-light fluorescent material still exist. Further expanding a blue light fluorescent material system, developing a deep blue light device with light color, service life and thermal stability, and starting from the synergy of material design and device preparation, the blue light fluorescent material is the only way for realizing the commercial application of the high-efficiency stable blue light fluorescent material.
Disclosure of Invention
The invention aims to introduce a new rigid electron-donating group into the structural system design of a blue fluorescent material, expand a blue fluorescent material system on the basis of the prior art through fine regulation and control of a compound structure, further improve the comprehensive performance of a blue electroluminescent device in the aspects of color coordinates, luminous efficiency, thermal stability, service life and the like, and solve the problem of high brightness (such as 1000 cd/m) of the blue fluorescent device2) The efficiency roll-off is serious, and the high-efficiency deep blue light emission is realized.
The polycyclic compound provided by the present invention is represented by the following chemical formula 1-1:
chemical formula 1-1:
wherein, X1、X2、X3、X4Are respectively identical or different and are independently O, S, N (R)7)、C(R8)(R9)、Si(R10)(R11) Any one of the above; a. b, c and d are the same or different and are independently 0 or 1, a and b are not all 0, c and d are not all 0, and when a, b, c or d is 0, X corresponding to a1、X2、X3Or X4The bridged 2 aromatic carbon sites are directly connected through a single bond;
are the same or different and are each independently empty or a single bond; r1-R6Are each identical or different and are independently selected from: hydrogen, a fluoro group, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms which is substituted or unsubstituted with at least one of a fluoro group, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms which is substituted or unsubstituted with at least one of a fluoro group, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an arylamine group having 6 to 30 carbon atoms which is substituted or unsubstituted with at least one of a fluoro group, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms; r7-R11Are each identical or different and are independently selected from: an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms which is substituted or unsubstituted with at least one of a fluoro group, a nitro group, a cyano group, and an alkyl group having 1 to 20 carbon atoms; r8And R9And R10And R11Can be independent of each other or linked to each other by a single bond to form a lipidCyclic or aromatic rings.
As a preferred embodiment, the chemical formula 1-1 is any one selected from the following structures represented by chemical formulas 2-1 to 2-8:
as a preferable embodiment, the alkyl group having 1 to 20 carbon atoms is any one of a methyl group, an ethyl group, and a tert-butyl group independently of one another; the alkoxy group having 1 to 20 carbon atoms is independently any one of a methoxy group and an ethoxy group; the alkylthio group having 1 to 20 carbon atoms is independently any one of a methylthio group and an ethylthio group; the aryl groups having 6 to 30 carbon atoms are independently of each other: phenyl substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, biphenyl substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, terphenyl substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, naphthyl substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl; the heteroaryl group having 3 to 30 carbon atoms is, independently of each other: carbazolyl substituted or unsubstituted with at least one of fluoro, cyano, nitro, methyl, ethyl, and tert-butyl, triazinyl substituted or unsubstituted with at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, and phenyl; the arylamine groups having 6 to 30 carbon atoms are, independently of one another: a diphenylamine-based compound which is substituted or unsubstituted with at least one of a fluoro group, a cyano group, a nitro group, a methyl group, an ethyl group, a tert-butyl group and a phenyl group, and a triphenylamine-based compound which is substituted or unsubstituted with at least one of a fluoro group, a cyano group, a nitro group, a methyl group, an ethyl group and a tert-butyl group.
As a preferred technical scheme, the R is1、R3、R4Independently of one another: hydrogen, fluoro, cyano, nitro, methyl, ethyl, tert-butyl, phenyl.
As a preferred technical scheme, the R is2Selected from: hydrogen, methyl, ethyl, tert-butyl, phenyl substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, biphenyl substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, diphenylamine substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, phenyl, carbazolyl substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, phenyl.
As a preferred technical scheme, the R is7Selected from: phenyl substituted or unsubstituted with at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, biphenyl substituted or unsubstituted with at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl;
as a preferred embodiment, R8And R9，R10And R11Identical to each other, independently of each other selected from: methyl, phenyl unsubstituted or substituted by at least one of fluoro, cyano, nitro, methyl, ethyl, and tert-butyl.
As a preferable embodiment, the chemical formula 1-1 is selected from any one of structures represented by the following compounds (1) to (270):
in a second aspect, the present invention provides a process for the preparation of a polycyclic compound comprising the steps of: (A1) the compound represented by (a) and the compound represented by (a2) are subjected to a wolmann reaction to obtain a compound represented by (A3), (A3) and the compound represented by (a4) are subjected to a wolmann reaction to obtain a compound represented by (a5), (a5) is subjected to a ring closure reaction to obtain a compound represented by the target chemical formula (1-1);
wherein the Wolman reaction is carried out in a reaction system of a palladium catalyst, a phosphine ligand, a solvent and alkali; the ring closing reaction is carried out in a reaction system of an organic lithium compound, halogenated boron and a solvent; said Y is1、Y3Independently of one another, I, Br, Cl or F; said Y is2H, Cl or Br.
The third aspect of the present invention provides an organic light emitting device, comprising: a first electrode; a second electrode disposed opposite to the first electrode; and an organic layer interposed between the first electrode and the second electrode, the organic layer including one or more polycyclic compounds selected from any one of claims 1 to 7.
As a preferable mode, the organic layer includes at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, wherein the light emitting layer is composed of the polycyclic compound alone, or the light emitting layer is composed of a light emitting host and a dopant, and the dopant includes one or more polycyclic compounds.
As a preferred technical solution, the organic light emitting device is an organic light emitting device of any one of a flat panel display device, a flexible display device, a flat panel lighting device, or a flexible lighting device.
The polycyclic compound provided by the application is formed by bonding arylamine, carbazole or dibenzo five-membered heterocyclic ring with boron as the center and the periphery, on one hand, resonance action between boron and nitrogen is utilized to inhibit non-radiative transition so as to realize ultra-narrow emission spectrum, on the other hand, high triplet state rigid groups such as dibenzofuran, dibenzothiophene, carbazole, fluorene and the like are favorable for blue light emission, electron donating groups which are large in volume and have weaker electron donating capability are condensed to be introduced into the polycyclic compound taking boron as the center, so that the overall thermal stability of the compound is favorably improved, simultaneously, a twisted structure is favorably formed in fluorescent molecules, Delta EST is reduced, light color is improved, and D-A type molecule design from the periphery to the center enables carriers in the molecules to more efficiently complete energy transfer and transfer, thereby reducing fluorescence quenching effect in devices and relieving the efficiency roll-off of the devices, therefore, when the polycyclic compound provided by the application is applied to an organic light-emitting device, the polycyclic compound can realize deep blue light emission, has comprehensive properties of light-emitting efficiency, service life, thermal stability and the like, is an excellent blue fluorescent material, and has remarkable advantages compared with other materials constructed by the same elements in common use and the prior art, no matter the polycyclic compound is used as a light-emitting object material of the organic light-emitting device or is independently used as a light-emitting layer of the organic light-emitting device.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or apparatus used are conventional products which are commercially available.
EXAMPLE 1 Synthesis of Compound (2)
After 11.80g of 6-bromobenzo [1,2-b:3,4-b' ] dibenzofuran, 7.14g of 2, 3-dichloro-N-phenylaniline, 5.77g of sodium tert-butoxide, 0.10g of tris-dibenzylideneacetone dipalladium, 0.05g of tris-tert-butylphosphine tetrafluoroborate and 100mL of toluene were charged into a reactor, they were mixed and stirred thoroughly, then they were heated under nitrogen protection for reflux reaction, the reaction mixture was cooled to room temperature, 5.08g of diphenylamine was charged, they were mixed and stirred thoroughly, under nitrogen protection for reflux reaction, the reaction mixture was cooled to room temperature, the reaction mixture was extracted with a mixture of water and dichloromethane, the organic phase was dried over magnesium sulfate and concentrated, and then purified and separated in a silica gel column using a mixed solvent of dichloromethane and petroleum ether at a ratio of 1:10 to obtain 12.60g of the compound represented by the following chemical formula (2a), the yield is 67%;
in a reactor, 6.27g of the compound represented by the above (2a) was dissolved in 50mL of a tert-butyl benzene solution, the reaction solution was cooled to-78 ℃, under the protection of nitrogen, slowly dropwise adding 48mL of 2.5M N-hexane tert-butyl lithium solution, keeping the temperature and stirring for 0.5-2h, adding 3.76g of boron tribromide, heating the reaction solution to room temperature and stirring for 0.5-2h, cooling the reaction solution to 0 ℃, adding 3.3mL of N, N-diisopropylethylamine, heating to 120 ℃ for reflux reaction, monitoring the completion of the reaction in a liquid phase, cooling to room temperature, adding acetic acid for quenching reaction, extracting the reaction solution by using a mixture of water and dichloromethane, drying an organic phase magnesium sulfate, concentrating, purifying and separating in a silica gel column by using a mixed solvent of 1:10 dichloromethane and petroleum ether, thus, 1.80g of a compound represented by the following chemical formula (2) was obtained in a yield of 30%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 600.80;
EXAMPLE 2 Synthesis of Compound (14)
By substituting 11.80g of 6-bromobenzo [1,2-b:3,4-b ' ] bibenzofuran in example 1 with 11.80g of 5-bromo-benzo [2,1-b:3,4-b ' ] bibenzofuran, 7.14g of 2, 3-dichloro-N-phenylaniline with 7.08g of 1, 2-dichloro-9H-carbazole, 5.08g of diphenylamine with 9.64g of bis ([1,1' -biphenyl ] -2-yl) amine, and the other synthetic procedures were the same as in example 1, 14.22g of the compound represented by the following chemical formula (14a) was obtained with a yield of 61%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 7.77g of the compound represented by (14a) in the present example to give 2.70g of the compound represented by the following formula (14) in a yield of 36%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 751.00;
EXAMPLE 3 Synthesis of Compound (21)
The same procedures as in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b '] bibenzofuran in example 1 with 11.80g of 5-bromobenzo [1,2-b:3,4-b' ] bibenzofuran, 7.14g of 2, 3-dichloro-N-phenylaniline with 7.08g of 1, 2-dichloro-9H-carbazole and 5.08g of diphenylamine with 5.02g of carbazole to give 12.15g of the compound represented by the following formula (14a) in a yield of 65%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 6.23g of the compound represented by (21a) in this example to give 1.97g of the compound represented by the following formula (21) in a yield of 33%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 596.72;
EXAMPLE 4 Synthesis of Compound (29)
The same procedures as in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b '] bibenzofuran in example 1 with 12.90g of 5-bromo-benzo [2,1-b ] benzothiophene [3,4-b' ] benzofuran to give 11.96g of the compound represented by the following formula (29a) in a yield of 62%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 6.43g of the compound represented by (29a) in the present example to give 1.90g of the compound represented by the following formula (29) in a yield of 31%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 616.25;
EXAMPLE 5 Synthesis of Compound (42)
The same procedures as in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b '] dibenzofuran in example 1 with 12.90g of 5-bromobenzo [1,2-b ] benzothiophene [3,4-b' ] benzofuran and 7.14g of 2, 3-dichloro-N-phenylaniline with 8.40g of N- (2, 3-dichlorophenyl) -2,4, 6-trimethylaniline and 5.08g of diphenylamine with 5.02g of carbazole to give 12.30g of the compound represented by the following formula (42a) in a yield of 60%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 6.83g of the compound represented by (42a) in the present example to give 2.30g of the compound represented by the following formula (42) in a yield of 35%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 656.50;
EXAMPLE 6 Synthesis of Compound (59)
The same procedures used in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b '] bibenzofuran in example 1 with 12.71g of 6-bromobenzo [1,2-b ] benzofuran [3,4-b' ] dimethylindene and 7.14g of 2, 3-dichloro-N-phenylaniline with 13.45g of 5- (9H-carbazol-9-yl) -2, 3-dichloro-N- (4-nitrophenyl) aniline to give 14.51g of the compound represented by the following formula (59a) in a yield of 56%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 8.63g of the compound represented by (59a) in this example to give 2.51g of the compound represented by the following formula (59) in a yield of 30%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 836.47;
EXAMPLE 7 Synthesis of Compound (61)
The same procedures as in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b '] bibenzofuran in example 1 with 12.71g of 5-bromobenzo [2,1-b ] benzofuran [3,4-b' ] dimethylindene and 7.14g of 2, 3-dichloro-N-phenylaniline with 14.08g of 2, 3-dichloro-5- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -N-phenylaniline, to obtain 13.53g of the compound represented by the following formula (61a) in a yield of 51%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 8.84g of the compound represented by (61a) in the present example to give 2.74g of the compound represented by the following formula (61) in a yield of 32%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 858.00;
EXAMPLE 8 Synthesis of Compound (66)
The same procedures as in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b '] dibenzofuran in example 1 with 12.71g of 5-bromobenzo [1,2-b ] dimethylindene [3,4-b' ] benzofuran, 7.14g of 2, 3-dichloro-N-phenylaniline with 7.08g of 1, 2-dichloro-9H-carbazole and 5.08g of diphenylamine with 5.92g of di-p-toluidine to give 13.04g of the compound represented by the following formula (66a) in a 64% yield;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 6.79g of the compound represented by (66a) described in this example, whereby 2.35g of the compound represented by the following formula (66) was obtained in a yield of 36%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 652.81;
EXAMPLE 9 Synthesis of Compound (86)
The same procedures as in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b '] bibenzofuran in example 1 with 14.43g of 6-bromobenzo [1,2-b ] benzofuran [3,4-b' ] phenylindole, 7.14g of 2, 3-dichloro-N-phenylaniline with 7.68g of 2, 3-dichloro-N- (4-fluorophenyl) aniline, and 5.08g of diphenylamine with 6.16g of di-p-fluoroaniline to give 12.93g of the compound represented by the following formula (86a) in a yield of 57%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 7.56g of the compound represented by (86a) described in this example, whereby 2.41g of the compound represented by the following formula (86) was obtained in a yield of 33%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 729.40;
EXAMPLE 10 Synthesis of Compound (107)
The same procedures as in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b '] bibenzofuran in example 1 with 17.09g of 5-bromobenzo [2,1-b ] benzofuran [3,4-b' ] biphenylindole, 7.14g of 2, 3-dichloro-N-phenylaniline with 7.08g of 1, 2-dichloro-9H-carbazole and 5.08g of diphenylamine with 5.02g of carbazole to give 13.92g of the compound represented by the following formula (107a) in a yield of 60%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 7.74g of the compound represented by (107a) in the present example to give 2.77g of the compound represented by the following formula (107) in a yield of 37%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 748.25;
EXAMPLE 11 Synthesis of Compound (108)
The same procedures used in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b '] bibenzofuran with 11.37g of 5-bromobenzo [1,2-b ] benzothiophene [3,4-b' ] benzothiophene and 7.14g of 2, 3-dichloro-N-phenylaniline with 11.71g of N- (2, 3-dichlorophenyl) - [1,1':3',1 '-terphenyl ] -5' -amine used in example 1 to give 13.14g of the compound represented by the following formula (108a) in a yield of 54%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 8.11g of the compound represented by (108a) described in this example, whereby 2.67g of the compound represented by the following formula (108) was obtained in a yield of 34%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 784.60;
EXAMPLE 12 Synthesis of Compound (118)
The same procedures as in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b '] bibenzofuran in example 1 with 11.37g of 5-bromobenzo [1,2-b ] benzothiophene [3,4-b' ] benzothiophene, 7.14g of 2, 3-dichloro-N-phenylaniline with 7.08g of 1, 2-dichloro-9H-carbazole and 5.08g of diphenylamine with 9.64g of biphenylamine to give 15.30g of the compound represented by the following formula (118a) in a yield of 63%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 8.09g of the compound represented by (118a) in this example to give 2.82g of the compound represented by the following formula (118) in a yield of 36%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 783.05;
EXAMPLE 13 Synthesis of Compound (131)
The same procedures used in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b '] bibenzofuran in example 1 with 13.28g of 6-bromobenzo [1,2-b ] benzothiophene [3,4-b' ] dimethylindene and 7.14g of 2, 3-dichloro-N-phenylaniline with 12.16g of 4, 5-dichloro-N1, N1, N3-triphenylbenzene-1, 3-diamine and obtaining 14.05g of the compound represented by the following formula (131a) in a yield of 56%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 8.36g of the compound represented by (131a) in this example to give 2.51g of the compound represented by the following formula (131) in a yield of 31%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 809.54;
EXAMPLE 14 Synthesis of Compound (136)
The same procedures as in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b' ] bibenzofuran in example 1 with 13.28g of 6-bromo-12, 12-dimethylfluorene [2,1-d ] thiophene and 7.14g of 2, 3-dichloro-phenylaniline with 7.08g of 1, 2-dichloro-9H-carbazole to give 12.41g of the compound represented by the following formula (136a) in a yield of 62%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 6.67g of the compound represented by (136a) in the present example to give 2.49g of the compound represented by the following formula (136) in a yield of 39%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 640.35;
EXAMPLE 15 Synthesis of Compound (162)
The same procedures as in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b' ] dibenzofuran in example 1 with 15.00g of 7-bromo-5-phenyl-5H-benzo [4,5] thieno [3,2-c ] carbazole, 7.14g of 2, 3-dichloro-N-phenylaniline with 7.56g of 2, 3-dichloro-N-p-tolylaniline, and 5.08g of diphenylamine with 5.92g of di-p-tolylamine to obtain 12.31g of the compound represented by the following formula (162a) in a yield of 53%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 7.74g of the compound represented by (162a) in the present example to give 2.40g of the compound represented by the following formula (162) in a yield of 32%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 747.83;
EXAMPLE 16 Synthesis of Compound (178)
By substituting 11.80g of 6-bromobenzo [1,2-b:3,4-b' ] bibenzofuran in example 1 with 15.00g of 7-bromo-5-phenyl-5H-benzo [4,5] thieno [3,2-c ] carbazole, 7.14g of 2, 3-dichloro-N-phenylaniline with 7.08g of 1, 2-dichloro-9H-carbazole, 5.08g of diphenylamine with 5.00g of carbazole, the other synthetic procedures were the same as in example 1, 12.86g of the compound represented by the following formula (178a) was obtained with a yield of 60%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 7.14g of the compound represented by (178a) described in this example, whereby 2.44g of the compound represented by the following formula (178) was obtained in a yield of 35%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 687.50;
EXAMPLE 17 Synthesis of Compound (198)
By substituting 11.80g of 6-bromobenzo [1,2-b:3,4-b' ] dibenzofuran in example 1 with 13.63g of 5-bromo-7, 7,12, 12-tetramethyl-7, 12-indolino [1,2-a ] fluorene, 7.14g of 2, 3-dichloro-N-phenylaniline with 7.89g of 4- ((2, 3-dichlorophenyl) amine) benzonitrile, 5.08g of diphenylamine with 8.38g of 3, 6-di-tert-butyl-9H-carbazole, the other synthetic procedures were the same as in example 1, whereby 14.40g of the compound represented by the following chemical formula (198a) was obtained in a yield of 59%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 8.14g of the compound represented by (198a) in the present example to give 2.41g of the compound represented by the following formula (198) in a yield of 31%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 787.66;
EXAMPLE 18 Synthesis of Compound (214)
The same procedures as in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b' ] dibenzofuran in example 1 with 15.34g of 6-bromo-7, 7-dimethyl-12-phenyl-7, 12-indolino [1,2-a ] carbazole and 7.14g of 2, 3-dichloro-N-phenylaniline with 7.08g of 1, 2-dichloro-9H-carbazole to give 13.72g of the compound represented by the following formula (214a) in a yield of 63%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 7.26g of the compound represented by (214a) in this example to give 2.65g of the compound represented by the following formula (214) in a yield of 38%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 699.50;
EXAMPLE 19 Synthesis of Compound (229)
The same procedures as in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b' ] dibenzofuran in example 1 with 15.34g of 6-bromo-12, 12-dimethyl-11-phenyl-11, 12-indolino [2,1-a ] carbazole, 7.14g of 2, 3-dichloro-N-phenylaniline with 7.08g of 1, 2-dichloro-9H-carbazole, and 5.08g of diphenylamine with 5.02g of carbazole, whereby 14.34g of the compound represented by the following formula (229a) was obtained in a yield of 66%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 7.24g of the compound represented by (229a) described above to give 2.50g of the compound represented by the following formula (229) in a yield of 36%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 697.58;
EXAMPLE 20 Synthesis of Compound (238)
By substituting 11.80g of 6-bromobenzo [1,2-b:3,4-b' ] dibenzofuran in example 1 with 13.84g of 6-bromo-5, 5-dimethyl-5H-silafluorene [2,3-g ] benzofuran, 7.14g of 2, 3-dichloro-N-phenylaniline with 8.89g of N- (2, 3-dichlorophenyl) -2,4, 6-trimethylaniline, 5.08g of diphenylamine with 6.34g of 2,4, 6-trimethyl-N-phenylaniline and by following the other synthetic procedures of example 1, 12.20g of the compound represented by the following formula (238a) was obtained in a yield of 54%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 7.53g of the compound represented by (238a) in this example to give 2.38g of the compound represented by the following formula (238) in a yield of 33%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 726.71;
EXAMPLE 21 Synthesis of Compound (248)
The same procedures as in example 1 were repeated except for substituting 11.80g of 6-bromobenzo [1,2-b:3,4-b' ] dibenzofuran in example 1 with 13.84g of 6-bromo-12, 12-dimethyl-12H-silafluorene [3,2-g ] benzofuran and 5.08g of diphenylamine with 5.02g of carbazole to give 12.80g of the compound represented by the following formula (248a) in a yield of 64%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 6.67g of the compound represented by (248a) in the present example to give 1.92g of the compound represented by the following formula (248) in a yield of 30%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 640.51;
EXAMPLE 22 Synthesis of Compound (260)
The same procedures as in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b' ] bibenzofuran in example 1 with 17.06g of 6-bromo-5, 12-diphenyl-5, 12-indolino [3,2-a ] carbazole, thereby obtaining 12.36g of a compound represented by the following chemical formula (260a) with a yield of 53%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 7.77g of the compound represented by (260a) in the present example to give 2.40g of the compound represented by the following formula (260) in a yield of 32%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 750.60;
EXAMPLE 23 Synthesis of Compound (270)
The same procedures as in example 1 were repeated except for replacing 11.80g of 6-bromobenzo [1,2-b:3,4-b' ] bibenzofuran in example 1 with 18.04g of 5-bromo-11, 12-di-p-tolyl-11, 12-indolino [2,3-a ] carbazole, 7.14g of 2, 3-dichloro-N-phenylaniline with 7.08g of 1, 2-dichloro-9H-carbazole, and 5.08g of diphenylamine with 5.02g of carbazole, thereby obtaining 13.46g of the compound represented by the following formula (270a) in a yield of 56%;
the same procedures used in example 1 were repeated except for replacing 6.27g of the compound represented by (2a) in example 1 with 7.77g of the compound represented by (260a) in the present example to give 2.86g of the compound represented by the following formula (270) in a yield of 37%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 774.30;
the embodiments of the present invention described in detail above are exemplary only for the purpose of illustrating the present invention and are not to be construed as limiting the present invention. The examples, which do not indicate specific techniques or conditions, are carried out according to techniques or conditions described in literature in the art.
Preparation of organic light-emitting device:
subjecting a glass substrate having an ITO film formed thereon to ultrasonic cleaning in isopropanol for 20 minutes
After washing, drying was performed on a hot plate heated to 200 ℃ for 10 minutes. After the UV ozone treatment was performed for 15 minutes, the ITO-coated glass substrate was mounted in a vacuum evaporator.
Forming N, N ' -bis [4- [ bis (3-methylphenyl) amino ] phenyl ] -N, N ' -diphenyl-biphenyl-4, 4' -diamine (DNTPD) with a film thickness of 70nm as a hole injection layer so as to cover the transparent anode;
forming N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) as a hole transport layer on the hole injection layer to a thickness of 25 nm;
on the hole transport layer, as a light emitting layer, binary vapor deposition was performed on 9, 10-bis (2-naphthyl) Anthracene (ADN) and the compound of the present application, or on 9, 10-bis (2-naphthyl) Anthracene (ADN) and the following comparative compound 1, or on 9, 10-bis (2-naphthyl) Anthracene (ADN) and the following comparative compound 2 at a vapor deposition rate of 97:3 to form a film thickness of 25 nm;
on the light-emitting layer, 8-hydroxyquinoline aluminum (Alq) was used as an electron-transporting layer3) And 2- [4- (9, 10-dinaphthalen-2-anthracen-2-yl) phenyl]-1-phenyl-1H-benzimidazole was evaporated at a ratio of 1:1 to form a film thickness of 30 nm.
On the electron transport layer, aluminum was deposited by evaporation to a thickness of 100nm to form a cathode, thereby completing the fabrication of an organic light emitting device.
The light-emitting characteristics of the produced light-emitting devices were measured by applying a dc voltage, and the results are summarized in table 1:
table 1 characterization of organic light emitting device properties
According to the test results in the table, the application realizes ultra-narrow emission spectrum by using the resonance effect between boron and nitrogen to inhibit non-radiative transition through the polycyclic compound formed by fine control and micro design, reduces the fluorescent quenching effect and the efficiency roll-off by designing D-A type molecules from the periphery to the center, and reduces the Delta E by introducing a new large-volume rigid electron-donating group, thereby being beneficial to forming a twisted structure in fluorescent molecules and reducing the Delta ESTImproving light color, and preparing an organic electroluminescent device by using the same, realizing deep blue light emission, and having significant technical advantages in starting voltage, luminous efficiency, thermal stability and service life compared with devices prepared by using compounds exemplified by comparative compound 1 and comparative compound 2 in the prior art,
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 polycyclic compound represented by the following chemical formula 1-1:
chemical formula 1-1:
wherein, X1、X2、X3、X4Are respectively identical or different and are independently O, S, N (R)7)、C(R8)(R9)、Si(R10)(R11) Any one of the above;
a. b, c and d are the same or different and are independently 0 or 1, a and b are not all 0, c and d are not all 0, and when a, b, c or d is 0, X corresponding to a1、X2、X3Or X4The bridged 2 aromatic carbon sites are directly connected through a single bond;
R1-R6are each identical or different and are independently selected from: hydrogen, fluoro, nitro, cyano, alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, alkylthio having 1 to 20 carbon atoms, aryl having 6 to 30 carbon atoms substituted or unsubstituted with at least one of fluoro, nitro, cyano, alkyl having 1 to 20 carbon atoms, heteroaryl having 3 to 30 carbon atoms substituted or unsubstituted with at least one of fluoro, nitro, cyano, alkyl having 1 to 20 carbon atoms, heteroaryl having 1 to 20 carbon atoms substituted or unsubstituted with at least one of fluoro, nitro, cyano, alkyl having 1 to 20 carbon atomsAn arylamine group having 6 to 30 carbon atoms;
R7-R11are each identical or different and are independently selected from: an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms which is substituted or unsubstituted with at least one of a fluoro group, a nitro group, a cyano group, and an alkyl group having 1 to 20 carbon atoms;
R8and R9And R10And R11Each of which may be independent of each other or may be linked to each other by a single bond to form an alicyclic or aromatic ring.
2. The polycyclic compound according to claim 1, wherein the chemical formula 1-1 is any one selected from the group consisting of structures represented by chemical formulas 2-1 to 2-8 below:
3. polycyclic compound according to claim 2, characterized in that the alkyl group having 1 to 20 carbon atoms is, independently of each other, any of methyl, ethyl, tert-butyl;
the alkoxy group having 1 to 20 carbon atoms is independently any one of a methoxy group and an ethoxy group;
the alkylthio group having 1 to 20 carbon atoms is independently any one of a methylthio group and an ethylthio group;
the aryl groups having 6 to 30 carbon atoms are independently of each other: phenyl substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, biphenyl substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, terphenyl substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, naphthyl substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl;
the heteroaryl group having 3 to 30 carbon atoms is, independently of each other: carbazolyl substituted or unsubstituted with at least one of fluoro, cyano, nitro, methyl, ethyl, and tert-butyl, triazinyl substituted or unsubstituted with at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, and phenyl;
the arylamine groups having 6 to 30 carbon atoms are, independently of one another: a diphenylamine-based compound which is substituted or unsubstituted with at least one of a fluoro group, a cyano group, a nitro group, a methyl group, an ethyl group, a tert-butyl group and a phenyl group, and a triphenylamine-based compound which is substituted or unsubstituted with at least one of a fluoro group, a cyano group, a nitro group, a methyl group, an ethyl group and a tert-butyl group.
4. The polycyclic compound of claim 2, wherein R is1、R3、R4Independently of one another: hydrogen, fluoro, cyano, nitro, methyl, ethyl, tert-butyl, phenyl;
R2selected from: hydrogen, methyl, ethyl, tert-butyl, phenyl substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, biphenyl substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, diphenylamine substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, phenyl, carbazolyl substituted or unsubstituted by at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, phenyl.
5. The polycyclic compound of claim 1, wherein R is7Selected from: quiltPhenyl substituted or unsubstituted with at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl, biphenyl substituted or unsubstituted with at least one of fluoro, cyano, nitro, methyl, ethyl, tert-butyl;
R8and R9，R10And R11Identical to each other, independently of each other selected from: methyl, phenyl unsubstituted or substituted by at least one of fluoro, cyano, nitro, methyl, ethyl, and tert-butyl.
6. The polycyclic compound according to any one of claims 1 to 5, wherein the chemical formula 1-1 is selected from any one of structures represented by the following compounds (1) to (270):
7. a process for the preparation of a polycyclic compound according to any one of claims 1 to 5, characterized by the following steps: (A1) the compound represented by (a) and the compound represented by (a2) are subjected to a wolmann reaction to obtain a compound represented by (A3), (A3) and the compound represented by (a4) are subjected to a wolmann reaction to obtain a compound represented by (a5), (a5) is subjected to a boronization ring-closing reaction to obtain a compound represented by the target chemical formula (1-1);
wherein the Wolman reaction is carried out in a reaction system of a palladium catalyst, a phosphine ligand, a solvent and alkali; the ring closing reaction is carried out in a reaction system of an organic lithium compound, halogenated boron and a solvent; said Y is1、Y3Independently of one another, I, Br, Cl or F; said Y is2H, Cl or Br.
8. An organic light emitting device, comprising:
a first electrode;
a second electrode disposed opposite to the first electrode; and
an organic layer sandwiched between the first electrode and the second electrode,
the organic layer comprises one or more polycyclic compounds selected from any one of claims 1 through 7.
9. The organic light emitting device according to claim 8,
the organic layer includes at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, wherein the light emitting layer is composed of the polycyclic compound of any one of claims 1 to 7 alone, or the light emitting layer is composed of a light emitting host and a dopant including one or more polycyclic compounds selected from any one of claims 1 to 7.
10. The organic light emitting device according to claim 9,
the organic light emitting device is an organic light emitting device of any one device of flat panel display equipment, flexible display equipment, flat panel lighting equipment or flexible lighting equipment.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115322104A (en) * | 2022-08-25 | 2022-11-11 | 北京八亿时空液晶科技股份有限公司 | Fluorene derivative and organic light-emitting element containing same |
| CN115353484A (en) * | 2022-07-05 | 2022-11-18 | 西北师范大学 | Synthetic method of 4-amino substituted carbazole, dibenzo [ b, d ] furan and fluorene derivatives |
| WO2024012365A1 (en) * | 2022-07-14 | 2024-01-18 | 清华大学 | Organic compound and use thereof |
| WO2024090353A1 (en) * | 2022-10-27 | 2024-05-02 | 東レ株式会社 | Compound, luminescent element material, luminescent element, display device, and illuminator |
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| KR20210095363A (en) * | 2020-01-23 | 2021-08-02 | 에스에프씨 주식회사 | Novel Organic compounds and Organic light emitting diode including the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20210095363A (en) * | 2020-01-23 | 2021-08-02 | 에스에프씨 주식회사 | Novel Organic compounds and Organic light emitting diode including the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115353484A (en) * | 2022-07-05 | 2022-11-18 | 西北师范大学 | Synthetic method of 4-amino substituted carbazole, dibenzo [ b, d ] furan and fluorene derivatives |
| WO2024012365A1 (en) * | 2022-07-14 | 2024-01-18 | 清华大学 | Organic compound and use thereof |
| CN115322104A (en) * | 2022-08-25 | 2022-11-11 | 北京八亿时空液晶科技股份有限公司 | Fluorene derivative and organic light-emitting element containing same |
| CN115322104B (en) * | 2022-08-25 | 2024-03-26 | 北京八亿时空液晶科技股份有限公司 | Fluorene derivative and organic light-emitting element comprising same |
| WO2024090353A1 (en) * | 2022-10-27 | 2024-05-02 | 東レ株式会社 | Compound, luminescent element material, luminescent element, display device, and illuminator |
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