CN109867646A - A kind of heterocyclic compound and its application - Google Patents
A kind of heterocyclic compound and its application Download PDFInfo
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- 150000002391 heterocyclic compounds Chemical class 0.000 title claims abstract description 53
- 125000003118 aryl group Chemical group 0.000 claims description 66
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 62
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 35
- 229910052805 deuterium Inorganic materials 0.000 claims description 35
- 125000004431 deuterium atom Chemical group 0.000 claims description 35
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 28
- 125000001072 heteroaryl group Chemical group 0.000 claims description 25
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 8
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 abstract description 62
- 150000001875 compounds Chemical class 0.000 abstract description 31
- 230000008901 benefit Effects 0.000 abstract description 20
- 230000005855 radiation Effects 0.000 abstract description 10
- 238000010494 dissociation reaction Methods 0.000 abstract description 7
- 230000005593 dissociations Effects 0.000 abstract description 7
- 238000005401 electroluminescence Methods 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 1
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- 230000006798 recombination Effects 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 15
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- 230000005281 excited state Effects 0.000 description 12
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000003513 alkali Substances 0.000 description 11
- 230000009286 beneficial effect Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 9
- 238000003775 Density Functional Theory Methods 0.000 description 8
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- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 7
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
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- 238000000859 sublimation Methods 0.000 description 6
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
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Abstract
The invention belongs to field of organic electroluminescent materials, a kind of heterocyclic compound and its application are disclosed.Heterocyclic compound provided by the present invention has structure shown in formula (B), the advantage is that: such compound can be used as the blue light or deep blue light emitting material of organic electroluminescence device, compensates for the deficiency of existing blue light emitting material；Such compound has very matched hole-electron transmission rate as luminescent material, is conducive to the luminous efficiency and device stability that improve material；In addition, such compound has very high bond dissociation energy, it is conducive to extend the driving service life of display device；With very high radiation transistion rate constant, it is conducive to extend the driving service life of organic light emitting diode device.
Description
Technical Field
The invention belongs to the field of organic electroluminescent materials, and particularly relates to a heterocyclic compound and application thereof.
Background
In recent years, organic light emitting diodes having electroluminescent properties have been intensively studied and developed. In the basic structure of an organic light emitting diode element, a thin film layer containing a light emitting material is disposed between a first electrode and a second electrode, and light emission is obtained from the light emitting material by applying a voltage to the element.
Due to the above-mentioned self-luminescence property of the organic light emitting diode device, compared to the liquid crystal display, the organic light emitting diode device has the advantages of high pixel visibility, no need of a backlight source, and the like, and thus is very suitable for being used as a flat panel display device, and is light, thin, and fast in response. In addition, since the organic light emitting diode element can also be in the form of a thin film, it is also possible to realize planar light emission of a large area using the organic light emitting diode and to serve as a surface light source of an illumination lamp.
The working principle of the organic light emitting diode is as follows: the driving is performed by injecting electrons from the cathode and holes from the anode into a thin film layer containing a light-emitting material between a pair of electrodes. The electrons injected from the cathode and the holes injected from the anode recombine in the thin film layer containing the light emitting material to form a molecular excited state, and the molecular excited state returns to the ground state after releasing energy. The excited state of the organic compound may be a singlet excited state or a triplet excited state, and light emission may be generated from either excited state.
The emission wavelength of the light emitting element is determined by the energy difference between the ground state and the excited state, i.e., the energy gap. Thus, by appropriate selection or modification of the molecular structure that produces light emission, light of any color can be obtained. When a light emitting device is manufactured using light emitting elements capable of emitting red, blue, and green light, which are three primary colors of light, the light emitting device is capable of displaying full color. Therefore, red, blue, and green light emitting materials are required for manufacturing a high-performance full-color light emitting device, and these light emitting materials are required to have good life and emission efficiency. In recent years, red and green luminescent materials excellent in performance have been obtained in the art. However, there is still room for development of a blue light emitting material having good emission lifetime and emission efficiency.
Disclosure of Invention
The present invention aims to overcome the above-mentioned disadvantages by providing a heterocyclic compound which can be used as a blue light-emitting material and has good emission efficiency and emission lifetime, and use thereof.
The purpose of the invention is realized by the following technical scheme:
embodiments of the present invention provide a heterocyclic compound having a structure represented by formula (B):
wherein Ar is1Selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups; r1-R8Each independently selected from hydrogen atom, deuterium atom, C1-C8 alkyl, substituted or unsubstituted C6-C30 aryl; a has a structure represented by formula (S1) or formula (S2):
x is selected from O or S; r9-R15Each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
Optionally, the C6-C30 heteroaryl is selected from dibenzothiophene or dibenzofuran; the substituted or unsubstituted C6-C30 aryl group is selected from structures of one of formulas (1-1) to (1-29):
alternatively, embodiments of the invention provide heterocyclic compounds having a structure represented by formula (B1):
wherein Ar is1Selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups; r1-R8Each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group; x is selected from O or S; r9-R15Each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
Alternatively, the heterocyclic compound provided by the embodiment of the present invention has a structure represented by formula (B1-1):
wherein Ar is1Selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups; x is selected from O or S; r9、R11、R14Each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
Alternatively, the heterocyclic compound provided by the embodiment of the present invention has a structure represented by formula (B1-2):
wherein Ar is1Selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups; x is selected from O or S; r11Selected from hydrogen atom, deuterium atom, C1-C8 alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C6-C30 heteroaryl.
Alternatively, the heterocyclic compound provided by the embodiment of the present invention has a structure represented by formula (B1-3):
wherein Ar is1、Ar2Each independently selected from a hydrogen atom, a substituted or unsubstituted C6-C30 aryl group; x is selected from O or S.
Alternatively, embodiments of the invention provide heterocyclic compounds having a structure represented by formula (B2):
wherein Ar is1Selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups; r1-R8Each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, substituted or unsubstitutedA C6-C30 aryl group; x is selected from O or S; r9-R15Each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
Alternatively, the heterocyclic compound provided by the embodiment of the present invention has a structure represented by formula (B2-1):
wherein Ar is1Selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups; x is selected from O or S; r9、R12、R14Each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
Alternatively, the heterocyclic compound provided by the embodiment of the present invention has a structure represented by formula (B2-2):
wherein Ar is1、Ar2Each independently selected from a hydrogen atom, a substituted or unsubstituted C6-C30 aryl group; x is selected from O or S; r12、R14Each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
Alternatively, the heterocyclic compound provided by the embodiment of the present invention has a structure represented by formula (B2-3):
wherein Ar is1Selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups; x is selected from O or S;R14、R16-R22each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group.
Alternatively, embodiments of the invention provide heterocyclic compounds having a structure selected from one of L1-L300:
embodiments of the present invention also provide an organic light emitting diode whose light emitting layer material contains the above heterocyclic compound.
Optionally, the heterocyclic compound is a host light-emitting material or a guest light-emitting material in a light-emitting layer of the organic light-emitting diode.
Embodiments of the present invention provide significant advantages over the prior art in that the heterocyclic compounds: (1) the compound can be used as a blue light (or deep blue light) luminescent material of an organic electroluminescent device, and makes up for the defects of the existing blue luminescent material. (2) With a very matched hole-electron transport ratio (i.e., -0.1 eV)<＝λh-λe<＝0.1eV) is beneficial to improving the luminous efficiency and the device stability of the material. (3) Has very high bond dissociation energy, and is favorable for prolonging the driving life of the display device. (4) Having a very high radiation transition rate constant Kr>107(s-1) And the drive service life of the organic light-emitting diode device is prolonged.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the following examples. However, it will be appreciated by those of ordinary skill in the art that numerous technical details are set forth in order to provide a better understanding of the present invention in its various embodiments. However, the technical solutions claimed in the claims of the present invention can be implemented without these technical details and with various changes and modifications based on the following embodiments.
Compound (I)
In some embodiments of the invention, heterocyclic compounds are provided having a structure represented by formula (B):
wherein Ar is1Selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups; r1-R8Each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group; a has a structure represented by formula (S1) or formula (S2):
x is selected from O or S; r9-R15Each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, substituted or unsubstitutedC6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl.
In some embodiments of the invention, the C6-C30 heteroaryl is selected from dibenzothiophene or dibenzofuran; the substituted or unsubstituted C6-C30 aryl is selected from one of the structures as shown in formulas (1-1) to (1-29):
in some embodiments of the invention, heterocyclic compounds are provided having a structure represented by formula (B1):
wherein Ar is1Selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups; r1-R8Each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group; x is selected from O or S; r9-R15Each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
In some embodiments of the invention, heterocyclic compounds are provided having a structure represented by formula (B1-1):
wherein Ar is1Selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups; x is selected from O or S; r9、R11、R14Each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
In some embodiments of the invention, heterocyclic compounds are provided having a structure represented by formula (B1-2):
wherein Ar is1Selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups; x is selected from O or S; r11Selected from hydrogen atom, deuterium atom, C1-C8 alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C6-C30 heteroaryl.
In some embodiments of the invention, heterocyclic compounds are provided having a structure represented by formula (B1-3):
wherein Ar is1、Ar2Each independently selected from a hydrogen atom, a substituted or unsubstituted C6-C30 aryl group; x is selected from O or S.
In some embodiments of the invention, heterocyclic compounds are provided having a structure represented by formula (B2):
Ar1selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups; r1-R8Each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group; x is selected from O or S; r9-R15Each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
In some embodiments of the invention, heterocyclic compounds are provided having a structure represented by formula (B2-1):
wherein Ar is1Selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups; x is selected from O or S; r9、R12、R14Each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
In some embodiments of the invention, heterocyclic compounds are provided having a structure represented by formula (B2-2):
Ar1、Ar2each independently selected from a hydrogen atom, a substituted or unsubstituted C6-C30 aryl group; x is selected from O or S; r12、 R14Each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
In some embodiments of the invention, heterocyclic compounds are provided having a structure represented by formula (B2-3):
wherein Ar is1Selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups; x is selected from O or S; r14、R16-R22Each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group.
In some embodiments of the invention, heterocyclic compounds are provided having a structure selected from one of L1-L300:
general synthetic route:
the specific embodiments of the present invention also provide the above-described preparation method, which is synthesized by the following general synthetic route:
the bromide of the anthracene derivative is chemically coupled to the organoboron of the dibenzofuran or dibenzothiophene derivative according to the Suzuki-Miyaura reaction using tetrakis (triphenylphosphine) palladium (0) as a catalyst.
Wherein,
Ar1selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups;
R1-R8each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group;
x is selected from O or S;
R9-R15each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
Synthesis example:
the following provides methods for preparing the compounds disclosed in the present invention. The present disclosure is not intended to be limited to any one of the methods recited herein. One skilled in the art can readily modify the methods described or utilize different methods to prepare one or more of the disclosed compounds. The following aspects are merely exemplary and are not intended to limit the scope of the present disclosure. The temperature, catalyst, concentration, reactant composition, and other process conditions may be varied, and appropriate reactants and conditions for the desired complex may be readily selected by one skilled in the art to which the present disclosure pertains.
CDCl on a Varian Liquid State NMR instrument3Or DMSO-d6Recording at 400MHz in solution1H profile, 13C NMR profile recorded at 100MHZ, chemical shift referenced to residual deuterated solvent. If CDCL3As solvent, tetramethylsilane (δ ═ 0.00ppm) was used as internal standard for recording1H NMR spectrum; 13C NMR spectra were recorded using DMSO-d6(δ 77.00ppm) as an internal standard. If it is to be H2When O (delta. 3.33ppm) is used as a solvent, the remaining H is used2O (delta. 3.33PPM) was recorded as an internal standard1H NMR spectrum; the 13CNMR profile was recorded using DMSO-d6(δ 39.52ppm) as an internal standard. The following abbreviations (or combinations thereof) are used for explanation1Multiplicity of H NMR: s is single, D is double, T is triple, Q is quadruple, P is quintuple, M is multiple, BR is wide.
EXAMPLE 1 preparation of L2
After a certain amount of D2 and K2 are added into a three-neck flask, a mechanical stirring rod is arranged, nitrogen is introduced for 20 minutes, and catalyst Pd (PPh) is added under the protection of nitrogen3)40.25-3 mol% of 2M aqueous alkali and 0.018mol of 2M aqueous alkali, heating and refluxing, reacting for 5-10 hours, filtering after reaction, washing with toluene and ethanol. And recrystallizing the dimethylbenzene to obtain powder with the purity of more than 99 percent. In order to further improve the purity of the L2, the L2 product with the purity of more than 99.5 percent can be obtained by one or more times of sublimation by a vacuum sublimation apparatus.
Using CDCL3As solvent tetramethylsilane (δ ═ 0.00ppm) was recorded as internal standard1H NMR spectrum.
1H NMR(400MHZ,DMSO-d6)：
7.32ppm(12H,p),7.38-7.41ppm(4H,t),7.48ppm(2H,d),7.54ppm(2H,d),7.63-7.71ppm(14H,m)。
Example 2 preparation of L5
After a certain amount of D5 and K5 are added into a three-neck flask, a mechanical stirring rod is arranged, nitrogen is introduced for 20 minutes, and catalyst Pd (PPh) is added under the protection of nitrogen3)40.25-3 mol% of 2M aqueous alkali and 0.018mol of 2M aqueous alkali, heating and refluxing, reacting for 5-10 hours, filtering after reaction, washing with toluene and ethanol. And recrystallizing the dimethylbenzene to obtain powder with the purity of more than 99 percent. In order to further improve the purity of the L5, the L5 product with the purity of more than 99.5 percent can be obtained by one or more times of sublimation by a vacuum sublimation apparatus.
Using CDCL3As solvent tetramethylsilane (δ ═ 0.00ppm) was recorded as internal standard1H NMR spectrum.
1H NMR(400MHZ,DMSO-d6)：
7.19-7.22ppm(4H,q),7.32ppm(12H,t),7.41-7.48ppm(8H,p),7.67ppm(8H,p)。
Example 3 preparation of L155
Adding a certain amount of D155 and K155 into a three-neck flask, installing a mechanical stirring rod, introducing nitrogen for 20 minutes, and adding a catalyst Pd (PPh) under the protection of the nitrogen3)40.25-3 mol% of 2M aqueous alkali and 0.018mol of 2M aqueous alkali, heating and refluxing, reacting for 5-10 hours, filtering after reaction, washing with toluene and ethanol. And recrystallizing the dimethylbenzene to obtain powder with the purity of more than 99 percent. In order to further improve the purity of the L155, a vacuum sublimation instrument is adopted to carry out sublimation for one time or more times, and an L155 product with the purity of more than 99.5 percent can be obtained.
Using CDCL3As solvent tetramethylsilane (δ ═ 0.00ppm) was recorded as internal standard1H NMR spectrum.
1H NMR(400MHZ,DMSO-d6)：
7.22ppm(2H,t),7.32-7.39ppm(14H,m),7.48-7.53ppm(6H,q),7.67-7.74ppm(10H,m)。
Example 4 preparation of L32
After a certain amount of D32 and K32 are added into a three-neck flask, a mechanical stirring rod is arranged, nitrogen is introduced for 20 minutes, and catalyst Pd (PPh) is added under the protection of nitrogen3)40.25-3mol percent of 2M aqueous alkali and 0.018mol percent of 2M aqueous alkali are heated and refluxed, reacted for 5-12 hours, filtered after reaction, washed by toluene and added with ethyl acetateAnd (5) washing with alcohol. And recrystallizing the dimethylbenzene to obtain powder with the purity of more than 99 percent. In order to further improve the purity of the L32, the L32 product with the purity of more than 99.5 percent can be obtained by one or more times of sublimation by a vacuum sublimation apparatus.
Using CDCL3As solvent tetramethylsilane (δ ═ 0.00ppm) was recorded as internal standard1H NMR spectrum.
1H NMR(400MHZ,DMSO-d6)：
1.67ppm(12H,s),7.28-7.41ppm(14H,m),7.48ppm(2H,d),7.55-7.60ppm(4H,q),7.67-6.71ppm(10H,m) ,6.84ppm(2H,d),7.77ppm(2H,s),,7.90ppm(2H,d)。
Example 5: preparation of L52
After a certain amount of D52 and K52 are added into a three-neck flask, a mechanical stirring rod is arranged, nitrogen is introduced for 30 minutes, and catalyst Pd (PPh) is added under the protection of nitrogen3)40.25-3 mol% of 2M aqueous alkali and 0.018mol of 2M aqueous alkali, heating and refluxing, reacting for 5-12 hours, filtering after reaction, washing with toluene and ethanol. And recrystallizing the dimethylbenzene to obtain powder with the purity of more than 99 percent. In order to further improve the purity of the L52, the L52 product with the purity of more than 99.5 percent can be obtained by one or more times of sublimation by a vacuum sublimation apparatus.
Using CDCL3As solvent tetramethylsilane (δ ═ 0.00ppm) was recorded as internal standard1H NMR spectrum.
1H NMR(400MHZ,DMSO-d6)：
1.67ppm(6H,s),7.13-7.19ppm(2H,m),7.28-7.49ppm(10H,m),7.55ppm(1H,d),7.60ppm(1H,q), 7.67-7.71ppm(5H,m),7.77ppm(1H,s),7.84ppm(1H,d),7.90ppm(1H,d)。
Example 6: preparation of L58
Adding a certain amount of D58 and 58K into a three-neck flask, installing a mechanical stirring rod, introducing nitrogen for 30 minutes, adding 40.25 mol% -3 mol% of catalyst Pd (PPh3) and 0.018mol of 2M alkali solution under the protection of nitrogen, heating and refluxing for 5-12 hours, carrying out suction filtration after reaction, washing with toluene and washing with ethanol. And recrystallizing the dimethylbenzene to obtain powder with the purity of more than 99 percent. In order to further improve the purity of the L58, the L58 product with the purity of more than 99.5 percent can be obtained by one or more times of sublimation by a vacuum sublimation apparatus.
Using CDCL3As solvent tetramethylsilane (δ ═ 0.00ppm) was recorded as internal standard1H NMR spectrum.
1H NMR(400MHZ,DMSO-d6)：
7.06-7.19ppm(13H,m),7.28-7.55ppm(15H,m),7.60ppm(1H,q),7.67-7.71ppm(4H,m),7.77ppm(1H,s), 8.84ppm(1H,d),7.90ppm(1H,d)。
It should be noted that, in addition to the compounds prepared in examples 1-6 above, other compounds provided by the present invention can also be prepared by following the principles, methods and procedures similar to examples 1-6, with reference to general synthetic routes.
Luminescence property
When the electronic structure of a fluorescent small-molecule compound is researched, the mutual influence among electrons is very important, the Density Functional Theory (DFT) is widely used for researching a pi conjugated system, and the result of researching the photoelectric property of the compound provided by the invention by adopting a DFT method is more accurate than that of other methods. The geometric structure of the compound molecules in the ground state, the cation state and the anion state is optimized by adopting the method of DFT// B3LYP/6-31G (d), and the geometric structure of the excited state of the compound is obtained by adopting the method of DFT// B3LYP/6-31G (d). The absorption and emission spectra of these compounds were calculated using the time-density functional theory (TDDFT) method on the basis of the ground state and excited state geometries. By the above calculation method, various properties of the compound under study can be obtained, including ionization energy IP, electron affinity EA, recombination energy λ, highest occupied orbital HOMO, lowest occupied orbital LUMO, and energy gap Eg.
It is very important for organic light emitting devices that holes and electrons can be injected and transported in an efficient balance. The ionization energy and electron affinity of a molecule are used to evaluate the injection capability of holes and electrons, respectively. Table 2 below lists the calculated vertical ionization energy IP (v) and adiabatic ionization energy IP (A), vertical electron affinity EA (v) and adiabatic electron affinity EA (A), hole extraction energy HEP and electron extraction energy EEP for some of the compounds. Vertical ionization energy ip (v) refers to the energy difference of cations and molecules in neutral molecular geometry; adiabatic ionization energy ip (a) refers to the difference in energy in neutral and cationic geometries; the vertical electron affinity ea (v) refers to the difference in energy in neutral and anionic geometries; adiabatic electron affinity, ea (a), refers to the difference in energy in neutral and anionic geometries; the hole extraction energy HEP refers to the energy difference between a molecule and a cation in the cation geometry; electron extraction energy, EEP, refers to the difference in energy between a molecule and an anion in anion geometry. Generally, for small molecule organic materials, the smaller the ionization energy, the easier the injection of holes; the greater the electron affinity, the easier the electron injection.
From a microscopic perspective, the transport mechanism of charges in organic thin films can be described as a process of self-transport. Wherein an electron or hole is transferred from one charged electron molecule to an adjacent neutral molecule. According to Marcus theory, the mobility of the charge can be expressed as:
wherein T represents temperature; v represents a pre-exponential factor and is a coupling matrix element between two types of particles; λ is the recombination energy; kb is boltzmann's constant. It is clear that λ and V are important factors in determining the value of Ket. Generally, the range of charge transfer in the amorphous state is limited, and the variation in V value is small. Therefore, the magnitude of mobility is mainly determined by λ in the index. The smaller λ, the greater the mobility. For convenience of study, the influence of external environment is ignored, and the main discussion is the internal recombination energy.
According to computational derivation, the recombination energy can be finally expressed as:
λhole＝IP(v)-HEP
λelectron＝EEP-EA(v)
in general, in organic materials, the energy of an S1 excited state is different from that of a T1 excited state due to different degrees of self-rotation, and the energy of ES1 is 0.5-1.0 ev greater than that of ET1, so that the luminous efficiency of a pure organic fluorescent material is low. The thermal delayed fluorescence TADF material separates the HOMO-LUMO orbital and reduces the electron exchange energy of the HOMO-LUMO orbital and the TAEST-0 can be realized theoretically due to unique molecular design. In order to effectively evaluate the thermal delayed fluorescence effect of the material, delta EST evaluation is carried out, and the difference value delta EST between the lowest singlet excitation energy Es and the lowest triplet excitation energy ET of the compound provided by the invention is obtained by using a TDDFT method.
f @ S1-S0, defined as the intensity of the transition matrix of the exciton at S1- > S0, and has the following meaning: the larger f @ S1-S0 means the larger transition radiation rate Kr of the exciton at S1- > S0; conversely, a smaller f @ S1-S0 means a smaller transition radiation rate Kr of the exciton at S1- > S0. If the transition radiation rate Kr of the exciton at S1- > S0 is larger, the transition non-radiation rate Knr of the exciton at S1- > S0 is reduced, which is advantageous in improving the light emitting efficiency of the material, and the exciton is either used for light radiation or is annihilated by non-radiation (e.g., thermally inactivated).
The HOMO level, LUMO level, electron cloud distribution of HOMO and LUMO, S1, T1 and Δ E of the compound provided by the present invention were calculated as aboveSTEnergy levels, Table 1 below in sectionsThe compound gives specific photophysical information data as an example:
TABLE 1 photophysical information data
According to the calculation result, the heterocyclic compound provided by the invention has a lower T1 energy level and a high S1 energy level (S1>2.7eV), and meanwhile, when the heterocyclic compound is used as a guest luminescent material, the internal quantum efficiency is up to 62.5%, and the photoelectric properties are favorable for the compound to have better photoelectric properties.
Another advantage of the heterocyclic compound provided by the present invention is that the provided compound achieves the characteristics of matched hole transport performance or electron transport performance (i.e., -0.1eV ═ λ h- λ e ═ 0.1eV) with very simple molecular design, which is beneficial to improving the luminous efficiency of the material and the stability of the device.
Table 2 below gives, as an example of some of the compounds, a detailed calculation table of IPV, IPA, EAV, EAA, HEP, EEP,. lambda.h,. lambda.e.
TABLE 2 IPV, IPA, EAV, EAA, HEP, EEP, λ h, λ e calculation Table
Judging from the calculated hole recombination energy and electron recombination energy, for the L1 molecule: [ electron recombination energy λ e-hole recombination energy λ h ] ═ 0.02eV, therefore, the L1 molecule is a bipolar organic photoelectric material with ideal hole/electron transport balance, which has the molecular benefit of balancing the hole/electron carrier transport balance of the OLED device, thereby improving the OLED luminous efficiency and lifetime.
For the L2 molecule: [ electron recombination energy λ e-hole recombination energy λ h ] ═ 0.03eV, therefore, the L2 molecule is a bipolar organic photoelectric material with ideal hole/electron transport balance, which has the molecular advantage of being beneficial to balance the transport balance of hole/electron carriers of the OLED device, thereby improving the luminous efficiency and lifetime of the OLED.
For the L3 molecule: [ electron recombination energy λ e-hole recombination energy λ h ] ═ 0.06eV, therefore, the L3 molecule is a bipolar organic photoelectric material with ideal hole/electron transport balance, which has the molecular benefit of balancing the hole/electron carrier transport balance of the OLED device, thereby improving the OLED luminous efficiency and lifetime.
For the L4 molecule: [ electron recombination energy λ e-hole recombination energy λ h ] ═ 0.03eV, therefore, the L4 molecule is a bipolar organic photoelectric material with ideal hole/electron transport balance, which has the molecular advantage of being beneficial to balance the transport balance of hole/electron carriers of the OLED device, thereby improving the luminous efficiency and lifetime of the OLED.
For the L5 molecule: [ electron recombination energy λ e-hole recombination energy λ h ] ═ 0.03eV, therefore, the L5 molecule is a bipolar organic photoelectric material with ideal hole/electron transport balance, which has the molecular advantage of being beneficial to balance the transport balance of hole/electron carriers of the OLED device, thereby improving the luminous efficiency and lifetime of the OLED.
For the L6 molecule: [ electron recombination energy λ e-hole recombination energy λ h ] ═ 0.02eV, therefore, the L6 molecule is a bipolar organic photoelectric material with ideal hole/electron transport balance, which has the molecular benefit of balancing the hole/electron carrier transport balance of the OLED device, thereby improving the OLED luminous efficiency and lifetime.
For the L7 molecule: [ electron recombination energy λ e-hole recombination energy λ h ] ═ 0.01eV, therefore, the L7 molecule is a bipolar organic photoelectric material with ideal hole/electron transport balance, which has the molecular advantage of being beneficial to balance the transport balance of hole/electron carriers of the OLED device, thereby improving the luminous efficiency and lifetime of the OLED.
For the L8 molecule: [ electron recombination energy λ e — hole recombination energy λ h ] ═ 0eV, therefore, L8 therefore, the L1 molecule is a bipolar organic photoelectric material with a very ideal hole/electron transport balance, which has the molecular advantage of being beneficial to balance the hole/electron carrier transport balance of the OLED device, thereby improving the OLED luminous efficiency and lifetime.
For the L32 molecule: [ electron recombination energy λ e-hole recombination energy λ h ] ═ 0.03eV, therefore, the L32 molecule is a bipolar organic photoelectric material with ideal hole/electron transport balance, which has the molecular advantage of being beneficial to balance the transport balance of hole/electron carriers of the OLED device, thereby improving the luminous efficiency and lifetime of the OLED.
For the L52 molecule: [ electron recombination energy λ e-hole recombination energy λ h ] ═ 0.03eV, therefore, the L52 molecule is a bipolar organic photoelectric material with ideal hole/electron transport balance, which has the molecular advantage of being beneficial to balance the transport balance of hole/electron carriers of the OLED device, thereby improving the luminous efficiency and lifetime of the OLED.
For the L58 molecule: [ electron recombination energy λ e-hole recombination energy λ h ] ═ 0.06eV, therefore, the L58 molecule is a bipolar organic photoelectric material with ideal hole/electron transport balance, which has the molecular benefit of balancing the hole/electron carrier transport balance of the OLED device, thereby improving the OLED luminous efficiency and lifetime.
Chemical stability:
quantum chemical calculations have been successfully applied to evaluate the properties of molecules in either the ground or excited states, and to elucidate the chemical and photochemical reaction pathways for the results of the experiments. The density functional theory DFT method to study the dissociation energy BDE of neutral/positive/negative OLED molecules has been accepted by the industry (reference Chemical differentiation in organic light-emitting devices and electronics for the Design of New Materials, adv. Mater.2013,25, 2114-2129).
The third advantage of the disclosed compounds is illustrated by the following preferred examples of L1/L2/L7/L8: very high chemical stability. As follows: the dissociation energy of relevant chemical bonds of neutral molecules/positive ions/negative ions of the material L1/L2/L7/L8 is far higher than the corresponding energy level S1/T1, and the heterocyclic compound provided by the invention has quite high chemical stability.
TABLE 3S 1/T1 (in kcal/mol) and BDE values for the materials
As can be seen from table 3, the BDE (chemical bond dissociation energy) of the heterocyclic compound provided by the present invention is much greater than the S1 energy level of the material under the conditions of neutral substance/positively charged species/negatively charged species. For example, the BDE dissociation energy of a negatively charged molecule of L1 >104(kcal/mol) > > S1 ═ 74(kcal/mol), such a molecule is very electrochemically stable, which is advantageous for maintaining a long lifetime. Similarly, L2/L7/L8 and other heterocyclic compounds provided by the invention have BDE (chemical bond dissociation energy) of the compounds which is far greater than the S1 energy level of the compounds under the conditions of neutral substances/positive charge species/negative charge species.
Fluorescence radiation transition rate:
the heterocyclic compound provided by the invention has the fourth advantages that: has a very high transition radiation rate constant Kr of S1- > S0. The transition radiation rate constants of S1- > S0 in Table 4 below for compound L1/L2/L7/L8/L32/L52/L58:
TABLE 4 fluorescence radiation transition Rate
| Material numbering | Fluorescent radiation Rate constant Kr (10)7/s) |
| L1 | 8.144110186 |
| L2 | 13.60979774 |
| L7 | 7.88156558 |
| L8 | 9.082609218 |
| L32 | 14.18857788 |
| L52 | 10.87927754 |
| L58 | 12.87617547 |
As can be seen from the data in table 4 above, the heterocyclic compound provided by the present invention has a very high fluorescence radiation transition rate constant, and this property is beneficial to improve the light radiation process of excitons on the heterocyclic compound, thereby enhancing the fluorescence efficiency and lifetime.
Device application
In some embodiments of the invention, the heterocyclic compound is used in organic light emitting diodes, organic crystal fields, organic solar cells and quantum dot light emitting diodes.
In some embodiments of the present invention, there is also provided an organic light emitting diode device, wherein a material of a light emitting layer of the organic light emitting diode device comprises the heterocyclic compound.
Organic light emitting diode device example
(1) The compound L32 of the invention is used as a guest material of an emitting layer of an OLED device
And constructing a multilayer device structure of ITO/HIL/HTL/light-emitting layer/ETL/EIL/cathode. To facilitate the understanding of the technical advantages and device principles of the present invention, the present invention is described in terms of the simplest device structure.
ITO/HIL(10nm)/HTL(30nm)/HTL(30nm)/HOST：L32,3wt％,30nm/ETL(30nm)/LiF(1nm)/Al。
TABLE 5 partial comparison of device Performance
Efficiency roll off, defined herein as 0.1mA/cm2Efficiency to 100mA/cm2Rate of change of performance.
As can be seen from the data in table 5, the OLED devices using the compound provided by the present invention all have relatively small performance roll-off, and the maximum EQE is greater than 5%, because L32 is a TTA material with hole transport capability comparable to electron transport capability.
(2) Part of the compound of the invention is used as a host material of a light-emitting layer of an OLED device
And constructing a multilayer device structure of ITO/HIL/HTL/light-emitting layer/ETL/EIL/cathode. To facilitate the understanding of the technical advantages and device principles of the present invention, the present invention is described in terms of the simplest device structure.
ITO/HIL(10nm)/HTL(80nm)/HTL(10nm)/L：BD001,6wt％,30nm/ETL(30nm)/LiF(1nm)/Al。
Here L is the main body and BD001 is a commercial fluorescent blue material.
TABLE 6 partial comparison of device Performance
As can be seen from the data in table 6 above, the EQE of the OLED device using the compound provided by the present invention is > 5%, because the material provided by the present invention has TTA effect, and can transfer the excess T1 energy to S1 by up-conversion for the light emission of the guest material BD 001.
When the singlet S1 energy level of the light emitting material is 2 times greater than its triplet energy level, a situation may occur in which two triplet excitons collide to generate a singlet exciton during the electroluminescence process, i.e., the TTA effect. At this time, 75% of the originally wasted T1 energy is transferred to the S1 energy through the collision manner, and 37.5% of the S1 energy is increased, so that the luminous efficiency of the material is improved. In this embodiment, the compound of the present invention (e.g. compound L11) is used as a host material of the light-emitting layer, and under the action of an electric field, the photophysical mechanism of the OLED is as follows: 1) the host material yielded 25% S1+ 75% T1; 2) 75% of the T1 energy of the host material is transferred to its S1 exciton by TTA effect, and the T1 of the host material is lower than the T1 of the guest, HTL and ETL materials, i.e. the triplet state is confined to T1 of the host material (T1 of the host material is lowest); 3) the energy of the host material S1 is completely transferred to the guest material S1 in the light-emitting layer; 4) s1 of the guest material is used for light emission, S1, guest- > S0, guest. Through the TTA effect, the luminous efficiency of the OLED is obviously improved, and the service life of the device is prolonged.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples of implementing the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in its practical application.
Claims (12)
1. A heterocyclic compound having a structure represented by formula (B):
wherein,
Ar1selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups;
R1-R8each independently selected from hydrogen atom, deuterium atom, C1-C8 alkyl, substituted or unsubstituted C6-C30 aryl group;
a has a structure represented by formula (S1) or formula (S2):
x is selected from O or S;
R9-R15each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
2. The heterocyclic compound according to claim 1, characterized in that the C6-C30 heteroaryl group is selected from dibenzothiophene or dibenzofuran; the substituted or unsubstituted C6-C30 aryl group is selected from structures of one of formulas (1-1) to (1-29):
3. the heterocyclic compound according to claim 1, which has a structure represented by formula (B1):
wherein,
Ar1selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups;
R1-R8each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group;
x is selected from O or S;
R9-R15each independently selected from hydrogen atom, deuterium atom, C1-C8 alkyl, substituted or unsubstituted C6-C30 aryl, substitutedOr unsubstituted C6-C30 heteroaryl.
4. The heterocyclic compound according to claim 3, which has a structure represented by formula (B1-1):
wherein,
Ar1selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups;
x is selected from O or S;
R9、R11、R14each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
5. The heterocyclic compound according to claim 3, which has a structure represented by formula (B1-2):
wherein,
Ar1selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups;
x is selected from O or S;
R11selected from hydrogen atom, deuterium atom, C1-C8 alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C6-C30 heteroaryl.
6. The heterocyclic compound according to claim 3, which has a structure represented by formula (B1-3):
wherein,
Ar1、Ar2each independently selected from hydrogenAn atomic, substituted or unsubstituted C6-C30 aryl group;
x is selected from O or S.
7. The heterocyclic compound according to claim 1, which has a structure represented by formula (B2):
wherein,
Ar1selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups;
R1-R8each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group;
x is selected from O or S;
R9-R15each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
8. The heterocyclic compound according to claim 7, which has a structure represented by formula (B2-1):
wherein,
Ar1selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups;
x is selected from O or S;
R9、R12、R14each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
9. The heterocyclic compound according to claim 7, which has a structure represented by formula (B2-2):
Ar1、Ar2each independently selected from a hydrogen atom, a substituted or unsubstituted C6-C30 aryl group;
x is selected from O or S;
R12、R14each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C6-C30 heteroaryl group.
10. The heterocyclic compound according to claim 7, which has a structure represented by formula (B2-3):
wherein,
Ar1selected from hydrogen atoms, substituted or unsubstituted C6-C30 aryl groups;
x is selected from O or S;
R14、R16-R22each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a substituted or unsubstituted C6-C30 aryl group.
11. The heterocyclic compound of claim 1, having a structure selected from one of L1-L300:
12. an organic light-emitting diode characterized in that a light-emitting layer of the organic light-emitting diode comprises the heterocyclic compound according to any one of claims 1 to 11.
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| EP3831819A1 (en) * | 2019-12-02 | 2021-06-09 | Samsung Electronics Co., Ltd. | Heterocyclic compound and organic light-emitting device including the same |
| CN112979597A (en) * | 2019-12-02 | 2021-06-18 | 三星电子株式会社 | Heterocyclic compound and organic light-emitting device including the same |
| WO2022017997A1 (en) | 2020-07-22 | 2022-01-27 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| WO2022017998A1 (en) | 2020-07-22 | 2022-01-27 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
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| WO2022214566A1 (en) | 2021-04-09 | 2022-10-13 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| CN113149943A (en) * | 2021-05-10 | 2021-07-23 | 吉林奥来德光电材料股份有限公司 | Fluorescent compound, preparation method thereof and organic electroluminescent device comprising same |
| CN113149943B (en) * | 2021-05-10 | 2023-08-22 | 吉林奥来德光电材料股份有限公司 | Fluorescent compound, preparation method thereof and organic electroluminescent device comprising fluorescent compound |
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