CN115197222A - Organic compound, application thereof and organic electroluminescent device comprising organic compound - Google Patents

Organic compound, application thereof and organic electroluminescent device comprising organic compound Download PDF

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CN115197222A
CN115197222A CN202210846717.2A CN202210846717A CN115197222A CN 115197222 A CN115197222 A CN 115197222A CN 202210846717 A CN202210846717 A CN 202210846717A CN 115197222 A CN115197222 A CN 115197222A
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CN115197222B (en
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段炼
曾旋
张东东
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Tsinghua University
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Abstract

The invention relates to a compound, application thereof and an organic electroluminescent device containing the compoundThe compound has the following structure, wherein X 1 And X 2 Each independently is N or B; ring A represents a benzene ring, a naphthalene ring or an anthracene ring; ring B and ring C each independently represent a benzene ring, a naphthalene ring or an anthracene ring; ring D and ring E each independently represent a C8-C60 fused aromatic hydrocarbon. The compound of the present invention shows excellent device performance and stability when used as a light emitting material in an OLED device. The invention also protects the organic electroluminescent device adopting the compound with the general formula.

Description

Organic compound, application thereof and organic electroluminescent device comprising organic compound
Technical Field
The invention relates to an organic compound, application thereof and an organic electroluminescent device containing the compound, belonging to the technical field of organic electroluminescence.
Background
Organic Light Emission Diodes (OLED) are a kind of devices with sandwich-like structure, which includes positive and negative electrode films and Organic functional material layers sandwiched between the electrode films. Because the OLED device has the advantages of high brightness, quick response, wide viewing angle, simple process, flexibility and the like, the OLED device is concerned in the technical field of novel display and novel illumination. At present, the technology is widely applied to display panels of products such as novel lighting lamps, smart phones and tablet computers, and further expands the application field of large-size display products such as televisions, and is a novel display technology with fast development and high technical requirements.
In order to prepare an OLED light-emitting device with lower driving voltage, better light-emitting efficiency and longer service life, the performance of the OLED device is continuously improved, the structure and the manufacturing process of the OLED device need to be innovated, and photoelectric functional materials in the OLED device need to be continuously researched and innovated, so that functional materials with higher performance can be prepared.
The Multiple Resonance (MR) effect enables the dye to have narrower fluorescence spectrum and higher fluorescence quantum yield, and plays an important role in improving the performance of the device. At present, multiple resonance effect is mainly generated through the induction of nitrogen atoms and boron atoms or carbonyl groups which are alternately connected, but the delayed fluorescence service life is longer, so that the stability problem is brought while the color purity of the material is improved, and the application of the material is limited. Therefore, how to prepare a multiple resonance material with better stability still has a challenge.
Disclosure of Invention
In order to solve the technical problems, the invention provides an organic compound with a brand new structure, which has a general formula shown as the following formula (I):
Figure BDA0003730919010000011
in formula (I), the dotted line represents a single bond linkage or no linkage; x 1 And X 2 Each independently is N or B;
ring A represents a benzene ring, a naphthalene ring or an anthracene ring; ring B and ring C each independently represent a benzene ring, a naphthalene ring or an anthracene ring; ring D and ring E each independently represent a C8 to C60 fused aromatic hydrocarbon;
said R is A 、R B 、R C 、R D And R E Each independently represents a substituent group from a single substituent group to the maximum permissible number of substituents, R A 、R B 、R C 、R D And R E Each independently selected from one of hydrogen, deuterium, halogen, carbonyl, carboxyl, nitro, cyano, amino, silicon base, substituted or unsubstituted chain alkyl of C1-C36, substituted or unsubstituted cycloalkyl of C3-C36, substituted or unsubstituted alkoxy of C1-C10, substituted or unsubstituted thioalkoxy of C1-C10, substituted or unsubstituted arylamino of C6-C30, substituted or unsubstituted heteroaryl of C3-C30, substituted or unsubstituted monocyclic aryl or condensed ring aryl of C6-C60, substituted or unsubstituted aryloxy of C6-C60 and substituted or unsubstituted heteroaryl of C5-C60;
the R is A 、R B 、R C 、R D And R E Each with the ring A, the ring B, the,Ring C, ring D and ring E are connected by a single bond, or R A 、R B 、R C 、R D And R E Each fused to the linking ring A, ring B, ring C, ring D, and ring E;
when the above R is A 、R B 、R C 、R D And R E When the substituent exists, the substituent group is independently selected from one of deuterium, halogen, nitro, cyano, amino, carbonyl, carboxyl, chain alkyl of C1-C30, cycloalkyl of C3-C30, alkoxy of C1-C10, thioalkoxy of C1-C10, arylamino of C6-C30, heteroarylamino of C3-C30, aryl of C6-C60, aryloxy of C6-C60 and heteroaryl of C5-C60.
Different from the traditional multiple resonance fluorescent dye, the invention provides a novel multiple resonance fluorescent dye based on an indolocarbazole-like structure. In the indole carbazole-like structure, nitrogen/boron atoms and carbon atoms have different electronegativities, so that the Lowest Unoccupied Molecular Orbital (LUMO) of a molecule is separated and locally distributed on the atoms, an obvious non-bond orbital characteristic is presented, and the vibration coupling and the structural relaxation of the molecule are effectively weakened. Meanwhile, the dye mainly comprises C-C bonds and C-N bonds and has higher bond energy, so that the molecules have higher chemical stability. In addition, the fused molecular structure of the five-membered ring and the six-membered ring can realize hybridization of non-bond orbitals and pi orbitals to different degrees. The method is favorable for regulating and controlling the excited state energy level and increasing the single triplet state energy level difference, thereby inhibiting the reverse intersystem crossing of triplet state excitons and accelerating the exciton dynamic process. Therefore, the compound has narrower spectral half-peak width and excellent fluorescence quantum yield.
Specifically, the compound adopts a mother nucleus structure shown in formula (I), wherein a ring A, a ring B and a ring C adopt aromatic rings such as benzene rings, naphthalene rings and the like, a ring D and a ring E adopt condensed aromatic hydrocarbons, and X is 1 And X 2 Each independently selected from B or N. Wherein the hetero atom X 1 And X 2 The para position of the ring A can enhance the electron synergistic effect and reduce the energy level of the molecule. Ring A, ring B, ring C and hetero atom X 1 And X 2 Form an indole carbazole skeleton of the typeThe LUMO orbitals are particularly beneficial to be distributed on atoms at intervals and locally, and multiple resonance effects are generated. The ring D, the ring E and the indole carbazole skeleton are condensed in a six-membered ring mode, so that the bond tension of the molecule can be reduced, and the stability is improved. In addition, ring D and ring E of fused aromatics have stronger pi orbital characteristics. After being condensed with an indole carbazole skeleton, the molecular orbital hybridizes with non-bond orbital and pi orbital characteristics of different degrees, so that multiple resonance effect and excited state regulation are realized, and higher color purity and excellent luminous efficiency are obtained.
In the present specification, the "substituted or unsubstituted" group may be substituted with one substituent, or may be substituted with a plurality of substituents, and when a plurality of substituents are present, different substituents may be selected from the group.
In the present specification, the expression of Ca to Cb means that the group has carbon atoms of a to b, and the carbon atoms do not generally include the carbon atoms of the substituents unless otherwise specified.
In the present specification, the expression of the "-" underlined loop structure indicates that the linking site is located at an arbitrary position on the loop structure where the linking site can form a bond.
In the present specification, "independently" means that the subject may be the same or different when a plurality of subjects are provided.
In the present specification, unless otherwise specified, the expression of a chemical element generally includes the concept of its isotope, for example, the expression of "hydrogen (H)" includes its isotope 1 H (protium or H), 2 The concept of H (deuterium or D); carbon (C) then comprises 12 C、 13 C, etc., will not be described in detail.
The heteroatom in the heteroaryl group in the present specification generally refers to an atom or group of atoms selected from B, N, O, S, P, si and Se, preferably N, O, S.
In the present specification, examples of the halogen include: fluorine, chlorine, bromine, iodine, and the like.
In the present specification, the substituted or unsubstituted C6-C60 aryl group includes monocyclic aryl groups and condensed ring aryl groups, and C6-C30 aryl groups are more preferable. By monocyclic aryl is meant that the molecule contains at least one phenyl group, and when the molecule contains at least two phenyl groups, the phenyl groups are independent of each other and are linked by a single bond, as exemplified by: phenyl, biphenyl, terphenyl, and the like. Specifically, the biphenyl group includes 2-biphenyl, 3-biphenyl, and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl. The fused ring aryl group means a group having at least two aromatic rings in a molecule, and the aromatic rings are not independent of each other but are fused to each other with two adjacent carbon atoms in common. Exemplary are as follows: naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl,
Figure BDA0003730919010000032
And mesityl and derivatives thereof. The naphthyl group includes a 1-naphthyl group or a 2-naphthyl group; the anthracene group is selected from 1-anthracene group, 2-anthracene group and 9-anthracene group; the fluorenyl is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the pyrenyl is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetracenyl is selected from the group consisting of 1-tetracenyl, 2-tetracenyl, and 9-tetracenyl. The fluorene derivative group is selected from 9,9-dimethylfluorenyl, 9,9-diethylfluorenyl, 9,9-dipropylfluorenyl, 9,9-dibutylfluorenyl, 9,9-dipentylfluorenyl, 9,9-dihexylfluorenyl, 9,9-diphenylfluorenyl, 9,9-dinaphthylfluorenyl, 9,9' -spirobifluorenyl and benzofluorenyl.
In the present specification, the substituted or unsubstituted C5-C60 heteroaryl includes monocyclic heteroaryl and fused heteroaryl, more preferably C5-C30 heteroaryl, and still more preferably C5-C15 heteroaryl. The monocyclic heteroaryl group means that at least one heteroaryl group is contained in the molecule, and when one heteroaryl group and another group (for example, aryl group, heteroaryl group, alkyl group, etc.) are contained in the molecule, the heteroaryl group and the other group are independently connected by a single bond, and examples of the monocyclic heteroaryl group include: furyl, thienyl, pyrrolyl, pyridyl and the like. The fused heteroaryl refers to a group which has at least one aromatic heterocyclic ring and one aromatic ring (aromatic heterocyclic ring or aromatic ring) in a molecule, and the two are not independent of each other but share two adjacent atoms which are fused with each other. Examples of fused heteroaryl groups include: benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, acridinyl, isobenzofuranyl, isobenzothienyl, benzocarbazolyl, azacarbazolyl, phenothiazinyl, phenazinyl, 9-phenylcarbazolyl, 9-naphthylcarbazolyl, dibenzocarbazolyl, indolocarbazolyl, and the like.
For the purpose of further explanation, said ring D in formula (I) may be represented by ring D 1 And ring d 2 Condensed to form, said ring E may be formed by ring E 1 And ring e 2 Are fused together. Wherein, ring d 1 Ring d 2 Ring e 1 And ring e 2 Each independently represents a C6-C30 aromatic ring.
The organic compound of the present invention, more preferably, has a structure represented by any one of the following formulae (1), (2) or (3):
Figure BDA0003730919010000031
in formulae (1) to (3), ring d 1 Ring d 2 Ring e 1 And ring e 2 Each independently represents a C6-C30 aromatic ring; said X is 1 、X 2 Ring A, ring B, ring C, R A 、R B 、R C 、R D And R E Are as defined in formula (I); the R is B 、R C 、R D And R E Each linked to the linking ring structure by a single bond or fused.
Preferably, in the above formula, ring a represents a benzene ring, a naphthalene ring or an anthracene ring, and ring B and ring C are both benzene rings; or, the ring A, the ring B and the ring C are all benzene rings.
The organic compound of the present invention, more preferably, has a structure represented by any one of the following formulae (4), (5) or (6):
Figure BDA0003730919010000041
in formulae (4) to (6), the X 1 、X 2 、R A 、R B 、R C 、R D And R E Are as defined in formula (I); the R is B 、R C 、R D And R E Each of which is linked to the attached ring structure by a single bond or fused.
Still preferably, in the above general formula, X is 1 And X 2 And is simultaneously an N atom; or, the X 1 And X 2 And at the same time is a B atom.
Still more preferably, in the above general formula, R is A 、R B 、R C 、R D And R E Each independently selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, and mixtures thereof pentafluoroethyl, 2,2,2-trifluoroethyl, phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthrenyl, benzophenanthrenyl, pyrenyl, bornyl, perylenyl, fluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, spirodiclorophenyl, and mixtures thereof dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-3532-quinolyl, benzo-7,8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, and pyridoxalylPyridinoimidazolyl, pyrazinoimidazolyl, quinoxalinyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthracenyl, phenanthrenyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazenanthryl, 2,7-diazepine, 2,3-diazepine, 1,6-diazepine, 1,8-diazepine, 4,5-diazepine, 4,5,9,10-tetraazaepine, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocaine, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4 benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5_ oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 9,9-dimethyl acridinyl, diarylamino, triarylamino, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, tetrahydropyrrole, piperidine, methoxypiperidine, silyl, or a combination of two substituent groups selected from the above;
more preferably, R is A 、R B 、R C 、R D And R E Each independently selected from one of hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, adamantyl, fluorine, trifluoromethyl, phenyl, trimethylphenyl, naphthyl, anthryl, furyl, tetrahydrofuryl, pyrrolyl, tetrahydropyrrolyl, thienyl, carbazolyl, triazinyl, pyridyl, quinolyl, acridinyl, cyano, methoxy, silyl, dimethylamino, triarylamino, fluorenyl, dibenzofuranyl, dibenzothienyl, or a combination of the above two substituents.
Further, the compound of the general formula (I) of the present invention may preferably be a compound of the following specific structure: n-1 to N-420. These compounds are representative only:
Figure BDA0003730919010000051
Figure BDA0003730919010000061
Figure BDA0003730919010000071
Figure BDA0003730919010000081
Figure BDA0003730919010000091
Figure BDA0003730919010000101
Figure BDA0003730919010000111
Figure BDA0003730919010000121
Figure BDA0003730919010000131
Figure BDA0003730919010000141
Figure BDA0003730919010000151
Figure BDA0003730919010000161
the present invention also provides an organic electroluminescent device comprising a substrate comprising a first electrode, a second electrode and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer comprises a compound represented by any one of the above general formula (i), general formula (1) to formula (6).
Specifically, embodiments of the present invention provide an organic electroluminescent device including a substrate, and an anode layer, a plurality of light emitting functional layers, and a cathode layer sequentially formed on the substrate; the light-emitting functional layer comprises a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and the light-emitting layer is arranged between the hole transport layer and the electron transport layer; among them, it is preferable that the light-emitting layer contains the compound represented by the general formula (i) or the general formula (1) to (6).
In addition, the present invention also protects an organic electroluminescent device containing an organic compound represented by any one of the above general formula (i), general formula (1) to general formula (6) for use in display and lighting devices.
When the compounds are applied to doping materials of a light-emitting layer of an organic electroluminescent device, the OLED also shows excellent device efficiency and stability. The organic compound meets the requirements of panel manufacturing enterprises on high-performance materials at present, and shows good application prospects.
The organic compound of the present invention exhibits excellent performance as an organic electroluminescent device, presumably for the following reasons:
the organic compound adopts a mother nucleus structure shown in a formula (I), wherein a ring A, a ring B and a ring C adopt aromatic rings such as benzene rings, naphthalene rings and the like, and a ring D and a ring E adopt condensed aromatic rings. Whole molecular structureThe relatively rigid plane can inhibit non-radiative transition of molecules. Furthermore, ring A, ring B, ring C and heteroatom X 1 、X 2 The skeleton of the indolocarbazole is formed, so that the molecule has stronger multiple resonance effect and shows excellent luminous efficiency. Finally, the condensed aromatic hydrocarbon ring D and the ring E are condensed with the indolocarbazole skeleton in a six-membered condensed mode, pi orbital characteristics are hybridized on the basis of not sacrificing the original non-bond orbital of the molecule, the single-triplet state energy level difference of the molecule is enlarged, and the multiple resonance effect and the exciton dynamics process are considered.
The compound has narrower spectral half-peak width, excellent fluorescence quantum yield and faster exciton kinetic process. The electroluminescent device prepared by the organic compound provided by the invention has higher color purity, excellent device performance and longer service life, can meet the requirements of panel manufacturing enterprises on high-performance materials at present, and shows good application prospect.
Detailed Description
The specific production method of the above-mentioned novel compound of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the production method of the present invention is not limited to these synthesis examples.
Basic chemical raw materials of various chemicals used in the present invention, such as reaction intermediates of petroleum ether, hydroiodic acid, acetonitrile, sodium chloride, methylene chloride, N-dimethylformamide, cuprous iodide, tetra-N-butylammonium chloride, tert-butylbenzene, boron tribromide, N-butyllithium, tetrahydrofuran, and the like, are commercially available from shanghai tatatake technologies ltd and shanghai bei medicine technology ltd. The mass spectrometer used for determining the following compounds used was a ZAB-HS type mass spectrometer (manufactured by Micromass, UK).
The synthesis of the compounds of the present invention is briefly described below. For X 1 And X 2 The molecules are nitrogen atoms, firstly cuprous iodide is used as a catalyst, tetra-N-butylammonium hydroxide is used as alkali, N, N-dimethylformamide is used as a solvent, and a Ullmann reaction is carried out at 120 ℃ to carry out a snap ring, so that the target compound can be obtained. For X 1 And X 2 Are respectively nitrogen atom and boron atomWhen different atoms exist in the molecule, the intermediate is obtained by carrying out a retaining ring by utilizing a Ullmann reaction catalyzed by cuprous iodide. Further, a lithium halide exchange is generated with the halogen of the intermediate using n-butyl lithium. Subsequently, boron tribromide is added to perform lithium-boron metal exchange, and then, a Lewis base such as N, N-diisopropylethylamine Yi Site is added to perform a Tandem borohybrid-Krafft Reaction (Tandem Bora-Friedel-Crafts Reaction), whereby the target compound can be obtained. For X 1 And X 2 The synthesis process is similar to the boron deduction process, the intermediate is respectively subjected to lithium halide exchange and lithium boron exchange reaction, and then subjected to boron hybridization friedel-crafts reaction in the presence of N, N-diisopropylethylamine to obtain the target compound.
More specifically, the following gives a synthetic method of a representative specific compound of the present invention.
Synthesis example 1:
Figure BDA0003730919010000181
synthesis of Compound N-1-1
Figure BDA0003730919010000182
8-bromo-1-naphthaldehyde (2.35g, 10.00mmol) and indole (1.17g, 10.00mmol) are sequentially added into a 100mL double-neck flask, 50mL of acetonitrile and 0.25mL of hydroiodic acid are added under the nitrogen atmosphere, and the reaction is stopped after 12 hours at 80 ℃. Cooled to room temperature, 200mL of dichloromethane were added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 3:2) as eluent to give N-1-1 (0.54 g) as a yellow powder.
Synthesis of Compound N-1
Figure BDA0003730919010000183
A100 mL two-necked round-bottomed flask was charged with intermediate N-1-1 (0.50g, 0.75mmol) and cuprous iodide (0.29g, 1.50mmol), respectively, and 25mL of N, N-dimethylformamide and 2.5mL of tetra-N-butylammonium hydroxide were sequentially charged under a nitrogen atmosphere. Then the temperature is increased to 120 ℃ for reaction for 24h. After completion of the reaction, the reaction mixture was cooled to room temperature, extracted with methylene chloride and water, and the organic phase was collected and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure and subjected to column chromatography to give the title compound N-1 (0.31g, 82% yield, 97% purity by HPLC analysis) as a black solid. MALDI-TOF-MS results: molecular ion peaks: 504.20 elemental analysis results: theoretical value: c,90.45; h,4.00; n,5.55 (%); experimental values: c,90.42; h,4.01; n,5.57 (%).
Synthetic example 2:
Figure BDA0003730919010000184
synthesis of Compound N-2-1
Figure BDA0003730919010000191
(8-chloronaphthalen-1-yl) boronic acid (4.12g, 20.00mmol), 1,5-dibromo-3,7-bis (2-chlorophenyl) naphthalene-2,6-diamine (5.37g, 10.00mmol), tetrakistriphenylphosphine palladium (0.69g, 0.60mmol) and potassium carbonate (6.90g, 50.00mmol) were added sequentially to a 250mL double-necked flask. 100mL of tetrahydrofuran and 25mL of water were added under a nitrogen atmosphere, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 2:1) as eluent to give N-2-1 (3.2 g) as a white powder.
Synthesis of Compound N-2
Figure BDA0003730919010000192
This example is essentially the same as the synthesis of compound N-1, except that: in this case, N-1-1 is changed to N-2-1. The title compound, N-2 (0.68g, 43% yield, 93% purity by HPLC analysis), was a black solid. MALDI-TOF-MS results: molecular ion peaks: 554.12 elemental analysis results: theoretical values are as follows: c,90.95; h,4.00; n,5.05 (%); experimental values: c,91.06; h,3.97; n,4.97 (%).
Synthetic example 3:
Figure BDA0003730919010000193
synthesis of Compound N-6-1
Figure BDA0003730919010000194
4,12-dibromo-5,11-indoline [3,2-b ] carbazole (4.12g, 10.00mmol), (8-bromonaphthalen-1-yl) boronic acid (5.50g, 22.00mmol), tetrakistriphenylphosphine palladium (69mg, 0.60mmol) and potassium carbonate (2.76g, 20.00mmol) were added sequentially to a 250mL double-necked bottle. Under a nitrogen atmosphere, 60mL of toluene, 20mL of ethanol and 10mL of water were added, and the reaction was stopped after 24 hours at 90 ℃. Cooled to room temperature, 200mL of dichloromethane were added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 5:2) as eluent to give N-6-1 (1.87 g) as a yellow powder.
Synthesis of Compound N-6
Figure BDA0003730919010000201
This example is essentially the same as the synthesis of compound N-1, except that: in this case, N-1-1 is changed to N-6-1. The target compound N-6 (0.78g, 88% yield, 96% purity by HPLC) was a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 504.16 elemental analysis results: theoretical value: c,90.45; h,4.00; n,5.55 (%); experimental values: c,90.47; h,4.05N,5.52 (%).
Synthetic example 4:
Figure BDA0003730919010000202
synthesis of Compound N-11-1
Figure BDA0003730919010000203
4,10-dibromo-5,11-indoline [3,2-b ] carbazole (4.12g, 10.00mmol), (8-bromonaphthalen-1-yl) boronic acid (5.50g, 22.00mmol), tetrakistriphenylphosphine palladium (69mg, 0.60mmol) and potassium carbonate (2.76g, 20.00mmol) were added sequentially to a 250mL double-necked flask. Under a nitrogen atmosphere, 60mL of toluene, 20mL of ethanol and 10mL of water were added, and the reaction was stopped after 24 hours at 90 ℃. Cooled to room temperature, 200mL of dichloromethane are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 5:2) as eluent to give N-11-1 (2.37 g) as a yellow powder.
Synthesis of Compound N-11
Figure BDA0003730919010000204
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is changed to N-11-1. The target compound N-11 (1.58g, 88% yield, 96% purity by HPLC) was a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 504.12 elemental analysis results: theoretical value: c,90.45; h,4.00; n,5.55 (%); experimental values: c,90.41; h,4.03N,5.56 (%).
Synthesis example 5:
Figure BDA0003730919010000211
synthesis of Compound N-16-1
Figure BDA0003730919010000212
This example is essentially the same as the synthesis of compound N-1-1, except that the indole was replaced with an equivalent amount of benzindole. The aimed compound N-16-1 (0.69 g) was a yellow solid.
Synthesis of Compound N-16
Figure BDA0003730919010000213
This example is essentially the same as the synthesis of compound N-1, except that: in this case, N-1-1 is changed to N-16-1. The target compound N-16 (0.42g, 89% yield, 92% purity by HPLC analysis) was a black solid. MALDI-TOF-MS results: molecular ion peaks: 604.21 elemental analysis results: theoretical value: c,91.37; h,4.00; n,4.63 (%); experimental values: c,91.32; h,4.01; n,4.67 (%).
Synthetic example 6:
Figure BDA0003730919010000214
synthesis of Compound N-21-1
Figure BDA0003730919010000221
This example is essentially the same as the synthesis of compound N-6-1, except that: in this case, the halogenated indolocarbazole derivative should be replaced by an equivalent amount of substance. This gave N-21-1 (1.44 g) as a yellow powder.
Synthesis of Compound N-21
Figure BDA0003730919010000222
This example is essentially the same as the synthesis of compound N-1, except that: in this case, N-1-1 is changed to N-21-1. The title compound, N-21 (0.58g, 76% yield, 97% purity by HPLC) was a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 604.16 elemental analysis results: theoretical value: c,91.37; h,4.00; n,4.63 (%); experimental values: c,91.43; h,3.98N,4.59 (%).
Synthetic example 7:
Figure BDA0003730919010000223
synthesis of Compound N-31-1
Figure BDA0003730919010000224
This example is essentially the same as the synthesis of compound N-1-1, except that: in this case, the aldehyde is replaced by others. The aimed compound N-31-1 (0.28 g) was a yellow solid.
Synthesis of Compound N-31
Figure BDA0003730919010000231
This example is essentially the same as the synthesis of compound N-1, except that: in this case, N-1-1 is replaced by N-31-1. The title compound, N-31 (0.13g, 59% yield, 94% purity by HPLC analysis), was a purple black solid. MALDI-TOF-MS results: molecular ion peaks: 604.14 elemental analysis results: theoretical value: c,91.37; h,4.00; n,4.63 (%); experimental values: c,91.33; h,4.06; n,4.61 (%).
Synthesis example 8:
Figure BDA0003730919010000232
synthesis of Compound N-34-1
Figure BDA0003730919010000233
This example is essentially the same as the synthesis of compound N-1-1, except that: in this case, an aldehyde is substituted for the substance. The titled compound N-34-1 (0.51 g) was a yellow solid.
Synthesis of Compound N-34
Figure BDA0003730919010000234
This example is essentially the same as the synthesis of compound N-1, except that: in this case, N-1-1 is changed to N-34-1. The target compound N-34 (0.25g, 75% yield, 94% purity by HPLC) was a black solid. MALDI-TOF-MS results: molecular ion peaks: 604.28 elemental analysis results: theoretical value: c,91.37; h,4.00; n,4.63 (%); experimental values: c,91.32; h,4.04; n,4.64 (%).
Synthetic example 9:
Figure BDA0003730919010000241
synthesis of Compound N-48-1
Figure BDA0003730919010000242
In a 100mL two-necked flask, N-11 (0.51g, 1.01mmol) was dissolved in 25mL of N, N-dimethylformamide. Cooled to 0 ℃ and N-bromosuccinimide (0.36g, 2.02mmol) was added in portions. After 24 hours of reaction under exclusion of light, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:2) as eluents to give N-48-1 (0.63 g) as a red powder.
Synthesis of Compound N-48
Figure BDA0003730919010000243
A25 mL two-necked flask was charged with N-48-1 (0.33g, 0.50mmol), phenylboronic acid (0.13g, 1.10mmol), tetratriphenylphosphine palladium (17mg, 0.015mmol) and potassium carbonate (0.17g, 1.25mmol) in this order. Under a nitrogen atmosphere, 4mL of tetrahydrofuran and 1mL of water were added, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:1) as eluent to give the target compound N-48 (0.28g, 76% yield, 98% purity by HPLC) as an orange solid. MALDI-TOF-MS results: molecular ion peaks: 656.25 elemental analysis results: theoretical value: c,91.44; h,4.30; n,4.27 (%); experimental values: c,91.45; h,4.31; n,4.25 (%).
Synthesis example 10:
Figure BDA0003730919010000251
synthesis of Compound N-55-1
Figure BDA0003730919010000252
This example is essentially the same as the synthesis of compound N-2-1, except that: in this case, an equivalent amount of amine is required for the replacement. The aimed compound N-55-1 (0.22 g) was a yellow solid.
Synthesis of Compound N-55-2
Figure BDA0003730919010000253
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is changed to N-55-1. N-55-2 (0.09 g) was obtained as a black solid.
Synthesis of Compound N-55-3
Figure BDA0003730919010000254
In a 100mL two-necked flask, N-55-2 (0.61g, 1.01mmol) was dissolved in 25mL of N, N-dimethylformamide. Cooled to 0 ℃ and N-bromosuccinimide (0.36g, 2.02mmol) was added in portions. After 24 hours of reaction under exclusion of light, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Recrystallizing with petroleum ether and methanol as solvent, and vacuum filtering to obtain black powder N-55-3 (0.47 g).
Synthesis of Compound N-55
Figure BDA0003730919010000261
A25 mL two-necked bottle was charged with N-55-3 (0.38g, 0.50mmol), phenylboronic acid (0.13g, 1.10mmol), tetratriphenylphosphine palladium (17mg, 0.015mmol), and potassium carbonate (0.17g, 1.25mmol) in this order. Under a nitrogen atmosphere, 4mL of tetrahydrofuran and 1mL of water were added, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:2) as eluents to give the target compound N-55 (0.13g, 68% yield, HPLC assay purity 98%) as a black solid. MALDI-TOF-MS results: molecular ion peaks: 756.25 elemental analysis results: theoretical value: c,92.04; h,4.26; n,3.70 (%); experimental values: c,92.07; h,4.24; n,3.69 (%).
Synthetic example 11:
Figure BDA0003730919010000262
synthesis of Compound N-66-1
Figure BDA0003730919010000263
In a 100mL two-necked flask, N-6 (0.51g, 1.01mmol) was dissolved in 25mL of N, N-dimethylformamide. The mixture was cooled to 0 ℃ and N-bromosuccinimide (0.18g, 1.01mmol) was added in portions. After 24 hours in the dark, 200mL of dichloromethane were added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:2) as eluent to give N-66-1 (0.42 g) as a red powder.
Synthesis of Compound N-66
Figure BDA0003730919010000264
A25 mL two-necked flask was charged with N-66-1 (0.29g, 0.50mmol), 2-pyridineboronic acid (0.065g, 0.55mmol), tetrakistriphenylphosphine palladium (17mg, 0.015mmol) and potassium carbonate (0.17g, 1.25mmol) in this order. Under a nitrogen atmosphere, 4mL of tetrahydrofuran and 1mL of water were added, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:1) as eluents to give the target compound N-66 (0.21g, 86% yield, 98% purity by HPLC) as a red solid. MALDI-TOF-MS results: molecular ion peaks: 581.19 elemental analysis results: theoretical value: c,88.79; h,3.99; n,7.22 (%); experimental values: c,88.77; h,3.99; n,7.24 (%).
Synthetic example 12:
Figure BDA0003730919010000271
synthesis of Compound N-68
Figure BDA0003730919010000272
A25 mL two-necked flask was charged with N-48-1 (0.33g, 0.50mmol), 2-pyridineboronic acid (0.13g, 1.10mmol), tetratriphenylphosphine palladium (17mg, 0.015mmol) and potassium carbonate (0.17g, 1.25mmol) in this order. Under a nitrogen atmosphere, 4mL of tetrahydrofuran and 1mL of water were added, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:2) as eluents to give the target compound N-68 (0.30g, 89% yield, 98% purity by HPLC) as a red solid. MALDI-TOF-MS results: molecular ion peaks: 658.25 elemental analysis results: theoretical value: c,87.52; h,3.98; n,8.51 (%); experimental values: c,87.54; h,3.96; n,8.50 (%).
Synthetic example 13:
Figure BDA0003730919010000273
synthesis of Compound N-71-1
Figure BDA0003730919010000274
A25 mL two-necked flask was charged with N-66-1 (0.29g, 0.50mmol), 1-pyrimidineboronic acid (0.065g, 0.55mmol), tetratriphenylphosphine palladium (17mg, 0.015mmol) and potassium carbonate (0.17g, 1.25mmol) in this order. Under a nitrogen atmosphere, 4mL of tetrahydrofuran and 1mL of water were added, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate were added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:1) as eluents to give the target compound N-71 (0.13g, 52% yield, 99% purity by HPLC) as a red solid. MALDI-TOF-MS results: molecular ion peaks: 584.15 elemental analysis results: theoretical value: c,87.52; h,3.98; n,8.51 (%); experimental values: c,87.52; h,3.98; n,8.50 (%).
Synthesis example 14:
Figure BDA0003730919010000281
synthesis of Compound N-83
Figure BDA0003730919010000282
A25 mL two-necked flask was charged with N-48-1 (0.33g, 0.50mmol), 4-cyanophenylboronic acid (0.16g, 1.10mmol), tetratriphenylphosphine palladium (17mg, 0.015mmol) and potassium carbonate (0.17g, 1.25mmol) in this order. Under a nitrogen atmosphere, 4mL of tetrahydrofuran and 1mL of water were added, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate were added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:2) as eluents to give the target compound N-83 (0.25g, 79% yield, 98% purity by HPLC) as a red solid. MALDI-TOF-MS results: molecular ion peaks: 706.21 elemental analysis results: theoretical values are as follows: c,88.37; h,3.71; n,7.93 (%); experimental values: c,88.34; h,3.73; n,7.93 (%).
Synthetic example 15:
Figure BDA0003730919010000283
synthesis of Compound N-92-1
Figure BDA0003730919010000291
In a 100mL two-necked flask, N-11 (0.51g, 1.01mmol) was dissolved in 25mL of N, N-dimethylformamide. The mixture was cooled to 0 ℃ and N-bromosuccinimide (0.18g, 1.01mmol) was added in portions. After 24 hours of reaction under exclusion of light, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:1) as eluent to give N-92-1 (0.43 g) as an orange powder.
Synthesis of Compound N-92
Figure BDA0003730919010000292
In a 100mL two-necked flask, N-92-1 (0.87g, 1.50mmol) and cuprous cyanide (0.40g, 4.4 mmol) were dissolved in 25mL 1-methylpyrrolidone. And under the protection of nitrogen, heating to 150 ℃ and reacting for 24 hours. After the reaction was completed, it was cooled to room temperature, and 200mL of methylene chloride was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:2) as eluents to give the target compound N-92 (0.55g, 77% yield, 96% purity by HPLC) as a red solid. MALDI-TOF-MS results: molecular ion peaks: 529.16 elemental analysis results: theoretical value: c,88.45; h,3.62; n,7.93 (%); experimental values: c,88.46; h,3.61; n,7.93 (%).
Synthetic example 16:
Figure BDA0003730919010000293
synthesis of Compound N-111-1
Figure BDA0003730919010000294
This example is essentially the same as the synthesis of compound N-1-1, except that: in this case, equal amounts of aldehyde are to be replaced. The objective compound, N-111-1 (0.68 g), was a yellow solid.
Synthesis of Compound N-111
Figure BDA0003730919010000301
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is changed to N-111-1. The title compound N-111 (0.50g, 95% yield, 97% purity by HPLC) was a black solid. MALDI-TOF-MS results: molecular ion peaks: 556.13 elemental analysis results: theoretical value: c,90.62; h,4.35; n,5.03 (%); experimental values: c,90.48; h,4.36; n,5.16 (%).
Synthetic example 17:
Figure BDA0003730919010000302
synthesis of Compound N-112-1
Figure BDA0003730919010000303
This example is essentially the same as the synthesis of compound N-6-1, except that: in this case, an equivalent amount of boron ester is substituted. This gave N-112-1 (1.72 g) as a pale yellow powder.
Synthesis of Compound N-112
Figure BDA0003730919010000304
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is changed to N-112-1. The target compound N-112 (0.68g, 57% yield, 95% purity by HPLC analysis) was a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 556.13 elemental analysis results: theoretical value: c,90.62; h,4.35; n5.03 (%); experimental values: c,90.55; h,4.39; n5.06 (%).
Synthetic example 18:
Figure BDA0003730919010000311
synthesis of Compound N-113-1
Figure BDA0003730919010000312
4,10-dibromo-5,11-indoline [3,2-b ] carbazole (4.12g, 10.00mmol), (6-bromo-1,2-dihydroethylnaphthalen-5-yl) boronic acid (5.70g, 22.00mmol), tetratriphenylphosphine palladium (69mg, 0.60mmol) and potassium carbonate (2.76g, 20.00mmol) were added sequentially to a 250mL double-necked bottle. Under a nitrogen atmosphere, 60mL of toluene, 20mL of ethanol and 10mL of water were added, and the reaction was stopped after 24 hours at 90 ℃. Cooled to room temperature, 200mL of dichloromethane were added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 5:2) as eluent to give N-113-1 (2.37 g) as a yellow powder.
Synthesis of Compound N-113
Figure BDA0003730919010000313
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is changed to N-113-1. The title compound N-113 (1.42g, 77% yield, 98% purity by HPLC) was a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 556.12 elemental analysis results: theoretical values are as follows: c,90.62; h,4.35; n,5.03 (%); experimental values: c,90.61; h,4.33N,5.06 (%).
Synthetic example 19:
Figure BDA0003730919010000314
synthesis of Compound N-114-1
Figure BDA0003730919010000321
In a 100mL two-necked flask, N-113 (0.56g, 1.01mmol) was dissolved in 25mL of N, N-dimethylformamide. Cooled to 0 ℃ and N-bromosuccinimide (0.36g, 2.02mmol) was added in portions. After 24 hours in the dark, 200mL of dichloromethane were added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:1) as eluent to give N-114-1 (0.52 g) as a red powder.
Synthesis of Compound N-114
Figure BDA0003730919010000322
A25 mL two-necked flask was charged with N-114-1 (0.36g, 0.50mmol), 2,4,6-trimethylphenylboronic acid (0.18g, 1.10mmol), tetratriphenylphosphine palladium (17mg, 0.015mmol), and potassium carbonate (0.17g, 1.25mmol) in this order. Under a nitrogen atmosphere, 4mL of tetrahydrofuran and 1mL of water were added, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:1) as eluent to afford the title compound N-114 (0.34g, 88% yield, 99% purity by HPLC) as an orange solid. MALDI-TOF-MS results: molecular ion peaks: 792.32 elemental analysis results: theoretical values are as follows: c,90.87; h,5.59; n,3.53 (%); experimental values: c,90.90; h,5.57; n,3.53 (%).
Synthesis example 20:
Figure BDA0003730919010000323
synthesis of Compound N-115-1
Figure BDA0003730919010000331
This example is essentially the same as the synthesis of compound N-1-1, except that: in this case, equal amounts of aldehyde are to be replaced. The aimed compound N-115-1 (0.22 g) was a yellow solid.
Synthesis of Compound N-115
Figure BDA0003730919010000332
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is changed to N-115-1. The target compound N-115 (0.10g, 57% yield, 96% purity by HPLC analysis) was a purple black solid. MALDI-TOF-MS results: molecular ion peaks: 651.18 elemental analysis results: theoretical value: c,93.98; h,3.87; n,2.15 (%); experimental values: c,93.95; h,3.83; n,2.21 (%).
Synthetic example 21:
Figure BDA0003730919010000333
synthesis of Compound N-146-1
Figure BDA0003730919010000334
This example is essentially the same as the synthesis of compound N-1-1, except that: in this case, equal amounts of indole were replaced. The titled compound N-146-1 (0.32 g) was a yellow solid.
Synthesis of Compound N-146
Figure BDA0003730919010000341
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is changed to N-146-1. The target compound N-146 (0.18g, 73% yield, 96% purity by HPLC analysis) was a black solid. MALDI-TOF-MS results: molecular ion peaks: 532.17 elemental analysis results: theoretical values are as follows: c,90.20; h,4.54; n,5.26 (%); experimental values: c,90.11; h,4.50; n,5.39 (%).
Synthetic example 22:
Figure BDA0003730919010000342
synthesis of Compound N-158-1
Figure BDA0003730919010000343
This example is essentially the same as the synthesis of compound N-1-1, except that: in this case, equal amounts of indole were replaced. The aimed compound N-158-1 (0.28 g) was a yellow solid.
Synthesis of Compound N-158
Figure BDA0003730919010000344
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is changed to N-158-1. The target compound N-158 (0.15g, 67% yield, 98% purity by HPLC analysis) was a black solid. MALDI-TOF-MS results: molecular ion peaks: 616.82 elemental analysis results: theoretical value: c,89.58; h,5.88; n,4.54 (%); experimental values: c,89.54; h,5.91; n,4.55 (%).
Synthetic example 23:
Figure BDA0003730919010000351
synthesis of Compound N-160-1
Figure BDA0003730919010000352
This example is essentially the same as the synthesis of compound N-1-1, except that: in this case, equal amounts of indole and aldehyde have to be replaced. The aimed compound N-160-1 (0.39 g) was a yellow solid.
Synthesis of Compound N-160
Figure BDA0003730919010000353
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is changed to N-160-1. The target compound N-160 (0.14g, 88% yield, 96% purity by HPLC analysis) was a black solid. MALDI-TOF-MS results: molecular ion peaks: 728.02 elemental analysis results: theoretical values are as follows: c,88.97; h,7.19; n,3.84 (%); experimental values: c,89.03; h,7.24; n,3.73 (%).
Synthetic example 24:
Figure BDA0003730919010000354
synthesis of Compound N-163-1
Figure BDA0003730919010000361
This example is essentially the same as the synthesis of compound N-11-1, and the specific synthesis process is that 4,12-dibromo-2,8-di-tert-butyl-5,11-indoline [3,2-b ] carbazole (5.24g, 10.00mmol), (8-bromonaphthalen-1-yl) boronic acid (5.50g, 22.00mmol), tetratriphenylphosphine palladium (70mg, 0.60mmol) and potassium carbonate (2.76g, 20.00mmol) are sequentially added to a 250mL double-necked flask. Under a nitrogen atmosphere, 60mL of toluene, 20mL of ethanol and 10mL of water were added, and the reaction was stopped after 24 hours at 90 ℃. Cooled to room temperature, 200mL of dichloromethane were added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 3:2) as eluent to give N-163-1 (3.11 g) as a yellow powder.
Synthesis of Compound N-163
Figure BDA0003730919010000362
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is changed to N-163-1. The title compound N-163 (0.95g, 83% yield, 96% purity by HPLC) was a deep red solid. MALDI-TOF-MS results: molecular ion peaks: 616.32 elemental analysis results: theoretical values are as follows: c,89.58; h,5.88; n,4.54 (%); experimental values: c,89.65; h,5.86N,4.49 (%).
Synthetic example 25:
Figure BDA0003730919010000363
synthesis of Compound N-168-1
Figure BDA0003730919010000364
This example is essentially the same as the synthesis of compound N-11-1, and the specific synthesis process is that 4,10-dibromo-2,8-di-tert-butyl-5,11-indoline [3,2-b ] carbazole (5.24g, 10.00mmol), (8-bromonaphthalen-1-yl) boronic acid (5.50g, 22.00mmol), tetratriphenylphosphine palladium (70mg, 0.60mmol) and potassium carbonate (2.76g, 20.00mmol) are sequentially added to a 250mL double-necked flask. Under a nitrogen atmosphere, 60mL of toluene, 20mL of ethanol and 10mL of water were added, and the reaction was stopped after 24 hours at 90 ℃. Cooled to room temperature, 200mL of dichloromethane are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 3:2) as eluent to give N-168-1 (3.11 g) as a yellow powder.
Synthesis of Compound N-168
Figure BDA0003730919010000371
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is changed to N-168-1. The title compound N-168 (0.95g, 83% yield, 96% purity by HPLC) was a deep red solid. MALDI-TOF-MS results: molecular ion peaks: 616.32 elemental analysis results: theoretical value: c,89.58; h,5.88; n,4.54 (%); experimental values: c,89.65; h,5.86N,4.49 (%).
Synthetic example 26:
Figure BDA0003730919010000372
synthesis of Compound N-172-1
Figure BDA0003730919010000373
This example is essentially the same as the synthesis of compound N-1-1, except that: in this case, equal amounts of indole were replaced. The aimed compound N-172-1 (1.14 g) was a yellow solid.
Synthesis of Compound N-172
Figure BDA0003730919010000381
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is changed to N-172-1. The target compound N-172 (0.79g, 80% yield, 95% purity by HPLC analysis) was a black solid. MALDI-TOF-MS results: molecular ion peaks: 772.31 elemental analysis results: theoretical values are as follows: c,90.12; h,6.26; n,3.62 (%); experimental values: c,90.15; h,6.27; n,3.58 (%).
Synthetic example 27:
Figure BDA0003730919010000382
synthesis of Compound N-187-1
Figure BDA0003730919010000383
This example is essentially the same as the synthesis of compound N-1-1, except that: in this case, equal amounts of aldehyde are to be replaced. The aimed compound N-187-1 (0.32 g) was a yellow solid.
Synthesis of Compound N-187
Figure BDA0003730919010000391
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is changed to N-187-1. The target compound N-187 (0.25g, 91% yield, 94% purity by HPLC) was a black solid. MALDI-TOF-MS results: molecular ion peaks: 668.88 elemental analysis results: theoretical value: c,89.78; h,6.03; n,4.19 (%); experimental values: c,89.63; h,6.09; n,4.28 (%).
Synthetic example 28:
Figure BDA0003730919010000392
synthesis of Compound N-201-1
Figure BDA0003730919010000393
In a 100mL two-necked flask, N-1 (0.51g, 1.01mmol) was dissolved in 25mL of methylene chloride. Cooled to 0 ℃ and N-bromosuccinimide (0.72g, 4.04mmol) was added portionwise. After 24 hours of reaction under exclusion of light, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:2) as eluent to give black powder N-201-1 (0.66 g).
Synthesis of Compound N-201
Figure BDA0003730919010000394
A25 mL two-necked bottle was charged with N-201-1 (0.39g, 0.50mmol), 2,4,6-trimethylbenzeneboronic acid (0.18g, 1.10mmol), tetrakistriphenylphosphine palladium (17mg, 0.015mmol), and potassium carbonate (0.17g, 1.25mmol) in that order. Under a nitrogen atmosphere, 4mL of tetrahydrofuran and 1mL of water were added, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:1) as eluents to give the target compound N-201 (0.18g, 53% yield, 93% HPLC analytical purity) as a black solid. MALDI-TOF-MS results: molecular ion peaks: 740.32 elemental analysis results: theoretical value: c,90.78; h,5.44; n,3.78 (%); experimental values: c,90.81; h,5.41; n,3.78 (%).
Synthetic example 29:
Figure BDA0003730919010000401
synthesis of Compound N-213-1
Figure BDA0003730919010000402
In a 100mL two-necked flask, N-11 (0.51g, 1.01mmol) was dissolved in 25mL of dichloromethane. Cooled to 0 ℃ and N-bromosuccinimide (0.72g, 4.04mmol) was added portionwise. After 24 hours of reaction under exclusion of light, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:2) as eluent to give black powder N-213-1 (0.70 g).
Synthesis of Compound N-213
Figure BDA0003730919010000403
A25 mL two-necked flask was charged with N-213-1 (0.39g, 0.50mmol), 2,4,6-trimethylphenylboronic acid (0.36g, 2.20mmol), tetratriphenylphosphine palladium (17mg, 0.015mmol) and potassium carbonate (0.17g, 1.25mmol) in this order. Under a nitrogen atmosphere, 4mL of tetrahydrofuran and 1mL of water were added, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:1) as eluents to give the target compound N-213 (0.25g, 62% yield, 95% purity by HPLC) as a black solid. MALDI-TOF-MS results: molecular ion peaks: 976.45 elemental analysis results: theoretical values are as follows: c,90.95; h,6.19; n,2.87 (%); experimental values: c,91.00; h,6.16; n,2.85 (%).
Synthetic example 30:
Figure BDA0003730919010000411
synthesis of Compound N-233-1
Figure BDA0003730919010000412
This example is essentially the same as the synthesis of compound N-1-1, except that: equal amounts of indole and aldehyde were replaced in this case. The aimed compound N-233-1 (0.36 g) was a yellow solid.
Synthesis of Compound N-233
Figure BDA0003730919010000413
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is changed to N-233-1. The title compound N-233 (0.13g, 79% yield, 95% purity by HPLC) was a black solid. MALDI-TOF-MS results: molecular ion peaks: 576.55 elemental analysis results: theoretical value: c,79.16; h,2.80; n,4.86 (%); experimental values: c,79.20; h,2.82; n,4.84 (%).
Synthetic example 31:
Figure BDA0003730919010000414
synthesis of Compound N-248-1
Figure BDA0003730919010000421
This example is essentially the same as the synthesis of compound N-6-1, except that: in this case, an equivalent amount of halogenated indole is required. This gave N-248-1 (1.66 g) as a yellow powder.
Synthesis of Compound N-248
Figure BDA0003730919010000422
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is changed to N-248-1. The title compound N-248 (0.61g, 49% yield, 95% analytical purity by HPLC) was a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 554.13 elemental analysis results: theoretical values are as follows: c,86.63; h,3.27; n10.10 (%); experimental values: c,86.60; h,3.26; n10.14 (%).
Synthetic example 32:
Figure BDA0003730919010000423
synthesis of Compound N-289-1
Figure BDA0003730919010000424
This example is essentially the same as the synthesis of compound N-1-1, except that: in this case, equal amounts of indole were replaced. The aimed compound N-289-1 (0.51 g) was a yellow solid.
Synthesis of Compound N-289
Figure BDA0003730919010000431
This example is essentially the same as the synthesis of compound N-1, except that: in this case, N-1-1 is replaced by N-289-1. The target compound N-289 (0.37g, 87% yield, 95% purity by HPLC) was a black solid. MALDI-TOF-MS results: molecular ion peaks: 838.40 elemental analysis results: theoretical values are as follows: c,88.76; h,4.57; n,6.68 (%); experimental values: c,88.70; h,4.55; n,6.75 (%).
Synthetic example 33:
Figure BDA0003730919010000432
synthesis of Compound N-294-1
Figure BDA0003730919010000433
In a 100mL two-necked flask, N-6 (0.51g, 1.01mmol) was dissolved in 25mL of dichloromethane. Cooled to 0 ℃ and N-bromosuccinimide (0.36g, 2.02mmol) was added in portions. After 24 hours of reaction under exclusion of light, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:2) as eluent to give black powder N-294-1 (0.49 g).
Synthesis of Compound N-294
Figure BDA0003730919010000434
Into a 100mL two-necked flask were added N-294-1 (6.62g, 10.00mmol), carbazole (3.34g, 20.00mmol), palladium acetate (224mg, 1.00mmol), tri-tert-butylphosphine tetrafluoroborate (870mg, 3.00mmol) and sodium tert-butoxide (1.92g, 20mmol) in this order. Under a nitrogen atmosphere, 50mL of anhydrous toluene was added, and the reaction was stopped after 24 hours at 110 ℃. Cooled to room temperature, 200mL of dichloromethane are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 2:3) as eluents to give the target compound N-294 (4.18g, 53% yield, 93% HPLC analytical purity) as a black solid. MALDI-TOF-MS results: molecular ion peaks: 834.32 elemental analysis results: theoretical value: c,89.19; h,4.10; n,6.71 (%); experimental values: c,89.22; h,4.05; n,6.73 (%).
Synthesis example 34:
Figure BDA0003730919010000441
synthesis of Compound N-299-1
Figure BDA0003730919010000442
In a 100mL two-necked flask, N-11 (0.51g, 1.01mmol) was dissolved in 25mL of dichloromethane. Cooled to 0 ℃ and N-bromosuccinimide (0.36g, 2.02mmol) was added in portions. After 24 hours in the dark, 200mL of dichloromethane were added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:2) as eluent to give black powder N-299-1 (0.55 g).
Synthesis of Compound N-299
Figure BDA0003730919010000443
This example is essentially the same as the synthesis of compound N-299, except that: in this example, N-294-1 is changed to N-299-1. The target compound N-299 (5.18g, 63% yield, HPLC analytical purity 97%) was obtained as a black solid. MALDI-TOF-MS results: molecular ion peaks: 834.32 elemental analysis results: theoretical value: c,89.19; h,4.10; n,6.71 (%); experimental values: c,89.24; h,4.07; n,6.69 (%).
Synthetic example 35:
Figure BDA0003730919010000444
synthesis of Compound N-314
Figure BDA0003730919010000451
This example is essentially the same as the synthesis of compound N-201, except that: in this case, equivalent amounts of boron ester and halogenated indole derivatives were replaced. The title compound N-314 (3.75g, 63% yield, 97% purity by HPLC) was obtained as a dark red solid. MALDI-TOF-MS results: molecular ion peaks: 986.39 elemental analysis results: theoretical value: c,90.04; h,4.29; n,5.68 (%); experimental values: c,90.14; h,4.23; n,5.64 (%).
Synthesis example 36:
Figure BDA0003730919010000452
synthesis of Compound N-324
Figure BDA0003730919010000453
This example is essentially the same as the synthesis of compound N-201, except that: in this example, 2,4,6-trimethylphenylboronic acid was replaced with an equivalent amount of 2-biphenylboronic acid. The target compound N-324 (0.18g, 53% yield, 93% analytical purity by HPLC) was a black solid. MALDI-TOF-MS results: molecular ion peaks: 808.30 elemental analysis results: theoretical value: c,92.05; h,4.49; n,3.46 (%); experimental values: c,92.01; h,4.51; n,3.48 (%).
Synthetic example 37:
Figure BDA0003730919010000454
synthesis of Compound N-329
Figure BDA0003730919010000461
This example is essentially the same as the synthesis of compound N-201, except that: in this case, equivalent amounts of boron ester and haloindolocarbazole derivatives were replaced. The title compound N-329 (0.33g, 46% yield, 97% analytical purity by HPLC) was a dark red solid. MALDI-TOF-MS results: molecular ion peaks: 808.27 elemental analysis results: theoretical value: c,92.05; h,4.49; n,3.46 (%); experimental values: c,92.06; h,4.53; n,3.41 (%).
Synthetic example 38:
Figure BDA0003730919010000462
synthesis of Compound N-341
Figure BDA0003730919010000463
This example is essentially the same as the synthesis of compound N-201, except that: in this case, equivalent amounts of boron ester and halogenated indolocarbazole derivatives were replaced. The title compound N-341 (0.49g, 49% yield, 95% purity by HPLC) was a dark red solid. MALDI-TOF-MS results: molecular ion peaks: 888.27 elemental analysis results: theoretical value: c,91.86; h,4.99; n,3.15 (%); experimental values: c,91.88; h,5.02; n,3.10 (%).
Synthetic example 39:
Figure BDA0003730919010000464
synthesis of Compound N-353-1
Figure BDA0003730919010000471
N-48-1 (0.57g, 0.50mmol) and cuprous cyanide (0.40g, 4.4 mmol) were added sequentially to a 25mL double-necked flask and dissolved in 25mL of 1-methylpyrrolidone. And under the protection of nitrogen, heating to 150 ℃ and reacting for 24 hours. After the reaction was completed, it was cooled to room temperature, and 200mL of methylene chloride was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 2:3) as eluents to give N-353-1 (0.39 g) as a red solid.
Synthesis of Compound N-353-2
Figure BDA0003730919010000472
In a 100mL two-necked flask, N-353-1 (0.56g, 1.01mmol) was dissolved in 25mL of dichloromethane. Cooled to 0 ℃ and N-bromosuccinimide (0.36g, 2.02mmol) was added in portions. After 24 hours of reaction under exclusion of light, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:2) as eluent to give a deep red powder N-353-2 (0.44 g).
Synthesis of Compound N-353
Figure BDA0003730919010000473
N-353-2 (0.36g, 0.50mmol), 9,9-dimethyl-4-fluoreneboric acid (0.26g, 1.10 mmol), tetrakistriphenylphosphine palladium (17mg, 0.015mmol) and potassium carbonate (0.17g, 1.25mmol) were added sequentially to a 25mL two-necked bottle. Under a nitrogen atmosphere, 4mL of tetrahydrofuran and 1mL of water were added, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:1) as eluents to give the target compound N-353 (0.40g, 85% yield, 98% purity by HPLC) as a deep red solid. MALDI-TOF-MS results: molecular ion peaks: 938.27 elemental analysis results: theoretical value: c,89.53; h,4.51; n,5.97 (%); experimental values: c,89.55; h,4.52; n,5.93 (%).
Synthetic example 40:
Figure BDA0003730919010000481
synthesis of Compound N-359-1
Figure BDA0003730919010000482
A25 mL two-necked flask was charged with N-66-1 (0.58g, 1.00mmol), 2,4,6-trimethylphenylboronic acid (0.18g, 1.10mmol), tetratriphenylphosphine palladium (17mg, 0.015mmol), and potassium carbonate (0.17g, 1.25mmol) in that order. Under a nitrogen atmosphere, 4mL of tetrahydrofuran and 1mL of water were added, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate were added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:1) as eluent to give N-359-1 (0.51 g) as a red solid.
Synthesis of Compound N-359-2
Figure BDA0003730919010000483
In a 100mL two-necked flask, N-359-1 (0.75g, 1.01mmol) was dissolved in 25mL of dichloromethane. Cooled to 0 ℃ and N-bromosuccinimide (0.36g, 2.02mmol) was added in portions. After 24 hours of reaction under exclusion of light, 200mL of dichloromethane was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:1) as eluent to give N-359-2 (0.55 g) as a red powder.
Synthesis of Compound N-359
Figure BDA0003730919010000484
Into a 25mL two-necked flask were added N-359-2 (0.39g, 0.50mmol), anthracen-9-yl-boronic acid (0.24g, 1.10mmol), tetrakistriphenylphosphine palladium (17mg, 0.015mmol), and potassium carbonate (0.17g, 1.25mmol) in this order. Under a nitrogen atmosphere, 4mL of tetrahydrofuran and 1mL of water were added, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 2:3) as eluents to give the target compound N-359 (0.23g, 45% yield, HPLC analytical purity 98%) as a deep red solid. MALDI-TOF-MS results: molecular ion peaks: 1097.38 elemental analysis results: theoretical values are as follows: c,91.86; h,4.31; n,3.83 (%); experimental values: c,91.88; h,4.33; n,3.79 (%).
Synthesis example 41:
Figure BDA0003730919010000491
synthesis of Compound N-366-1
Figure BDA0003730919010000492
A250 mL two-necked flask was charged with 1-naphthoborate (5.08g, 20.00mmol), 2',3',5',6' -tetrabromo-1,1 ',4,1 "-terphenyl (5.42g, 10.00mmol), tetrakistriphenylphosphine palladium (0.69g, 0.60mmol) and potassium carbonate (6.90g, 50.00mmol) in that order. 100mL of tetrahydrofuran and 25mL of water were added under a nitrogen atmosphere, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 5:1) as eluent to give N-366-1 (4.4 g) as a pale yellow powder.
Synthesis of Compound N-366
Figure BDA0003730919010000493
A solution of N-butyllithium (10mL, 2.50M, 25.00mmol) was slowly added to a solution of N-366-1 (3.20g, 5.00mmol) in t-butylbenzene (80 mL) at 0 ℃ and then the temperature was sequentially raised to 60 ℃ for each reaction for 3 hours. After the reaction, the temperature is reduced to-30 ℃, boron tribromide (6.26g, 25.00mmol) is slowly added, and the stirring is continued for 0.5 hour at room temperature. N, N-diisopropylethylamine (4.83g, 37.5 mmol) was added at room temperature and the reaction was continued at 145 ℃ for 5 hours and stopped. The reaction was cooled to room temperature, extracted with dichloromethane and water, and the organic phase was collected and dried over anhydrous sodium sulfate. After the organic phase was concentrated under reduced pressure, column chromatography was carried out using petroleum ether and dichloromethane (petroleum ether: dichloromethane = 1:1) as eluent to obtain the objective compound N-366 (0.43g, 17% yield, HPLC analytical purity 97%) as a black solid. MALDI-TOF-MS results: molecular ion peaks: 498.18 elemental analysis results: theoretical values are as follows: c,91.61; h,4.05 (%); experimental values: c,91.53; h,4.03 (%).
Synthesis example 42:
Figure BDA0003730919010000501
synthesis of Compound N-370-1
Figure BDA0003730919010000502
This example is essentially the same as the synthesis of compound N-366-1, and the specific process is: 1,8-dibromonaphthalene (2.84g, 10.00mmol), 1,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9-hydro-carbazole (4.19g, 10.00mmol), tetratriphenylphosphine palladium (0.36g, 0.30mmol) and potassium carbonate (3.46g, 25.00mmol) were added sequentially to a 250mL two-necked flask. 100mL of tetrahydrofuran and 24mL of water were added under a nitrogen atmosphere, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 2:1) as eluent to give N-370-1 (2.7 g) as a white solid.
Synthesis of Compound N-370-2
Figure BDA0003730919010000503
This example is essentially the same as the synthesis of compound N-366-1, and the specific procedure is as follows: a100 mL double-necked bottle was charged with 1-bromo-8- (3-bromobenzene) naphthalene (1.80g, 5.00mmol), N-370-1 (2.49g, 5.00mmol), tetrakis triphenylphosphine palladium (0.18g, 0.15mmol) and potassium carbonate (1.73g, 12.50mmol) in that order. Under a nitrogen atmosphere, 50mL of tetrahydrofuran and 12mL of water were added, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 100mL of ethyl acetate was added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 3:2) as eluent to give N-370-2 (1.8 g) as a yellow solid.
Synthesis of Compound N-370-3
Figure BDA0003730919010000504
This example is essentially the same as the synthesis of compound N-1, except that: in this case, N-1-1 is replaced by N-370-2 of equal mass. The aimed compound N-370-3 (1.3 g) was a yellow powder.
Synthesis of Compound N-370
Figure BDA0003730919010000511
This example is essentially the same as the synthesis of compound N-366, except that: in this example, N-366-1 is replaced by N-370-3. The target compound N-370 (0.15g, 16% yield, 96% purity by HPLC analysis) was a red solid. MALDI-TOF-MS results: molecular ion peaks: 501.13 elemental analysis results: theoretical value: c,91.03; h,4.02; n,2.79 (%); experimental values: c,91.09; h,4.07; n,2.72 (%).
Synthetic example 43:
Figure BDA0003730919010000512
synthesis of Compound N-373-1
Figure BDA0003730919010000513
This example is essentially the same as the synthesis of compound N-366-1, except that: in this case, an equivalent amount of halide is replaced. The title compound, N-373-1 (4.5 g), was a pale yellow solid.
Synthesis of Compound N-373
Figure BDA0003730919010000514
This example is essentially the same as the synthesis of compound N-366, except that: in this example, N-366-1 is replaced by N-373-1. The title compound N-373 (0.37g, 25% yield, 97% purity by HPLC) was an orange solid. MALDI-TOF-MS results: molecular ion peaks: 610.23 elemental analysis results: theoretical value: c,90.51; h,5.94 (%); experimental values: c,90.56; h,5.96 (%).
Synthetic example 44:
Figure BDA0003730919010000521
synthesis of Compound N-374-1
Figure BDA0003730919010000522
This example is essentially the same as the synthesis of compound N-366-1, except that: equal amounts of boron ester and halide were replaced in this case. The aimed compound N-374-1 (3.8 g) was a yellow solid.
Synthesis of Compound N-374-2
Figure BDA0003730919010000523
This example is essentially the same as the synthesis of compound N-1, except that: in this case, N-1-1 is replaced by N-374-1 of equal mass. The aimed compound N-374-2 (2.1 g) was an orange solid.
Synthesis of Compound N-374
Figure BDA0003730919010000524
This example is essentially the same as the synthesis of compound N-366, except that: in this example, N-366-1 is replaced by N-374-2. The target compound N-374 (0.25g, 23% yield, 98% purity by HPLC) was a black solid. MALDI-TOF-MS results: molecular ion peaks: 613.26 elemental analysis results: theoretical value: c,90.04; h,5.91; n,2.28 (%); experimental values: c,89.95; h,5.95; n,2.32 (%).
Synthetic example 45:
Figure BDA0003730919010000531
synthesis of Compound N-386-1
Figure BDA0003730919010000532
This example is essentially the same as the synthesis of compound N-366-1, except that: in this case, an equivalent amount of boron ester was replaced. The aimed compound, N-386-1 (3.2 g), was a white solid.
Synthesis of Compound N-386
Figure BDA0003730919010000533
This example is essentially the same as the synthesis of compound N-366, except that: in this example, N-366-1 would need to be replaced with N-386-1. The title compound N-386 (0.17g, 13% yield, 97% purity by HPLC) was a black solid. MALDI-TOF-MS results: molecular ion peaks: 550.27 elemental analysis results: theoretical values are as follows: c,91.67; h,4.40 (%); experimental values: c,91.60; h,4.45 (%).
Synthesis example 46:
Figure BDA0003730919010000534
synthesis of Compound N-392-1
Figure BDA0003730919010000541
This example is essentially the same as the synthesis of compound N-366-1, except that: in this case, equal amounts of boron ester and halide are replaced. The aimed compound N-392-1 (2.7 g) was a white solid.
Synthesis of Compound N-392
Figure BDA0003730919010000542
This example is essentially the same as the synthesis of compound N-366, except that: in this example, N-366-1 is replaced by N-392-1. The title compound N-392 (0.13g, 29% yield, 98% purity by HPLC) was a red solid. MALDI-TOF-MS results: molecular ion peaks: 734.31 elemental analysis results: theoretical values are as follows: c,91.57; h,5.49 (%); experimental values: c,91.62; h,5.46 (%).
Synthetic example 47:
Figure BDA0003730919010000543
synthesis of Compound N-396-1
Figure BDA0003730919010000544
This example is essentially the same as the synthesis of compound N-366-1, except that: in this case, an equivalent amount of the halogen compound should be replaced. The title compound, N-396-1 (3.1 g), was a pale yellow solid.
Synthesis of Compound N-396
Figure BDA0003730919010000551
This example is essentially the same as the synthesis of compound N-366, except that: in this example, N-366-1 is replaced by N-396-1. The title compound N-396 (0.28g, 17% yield, 93% purity by HPLC) was a black solid. MALDI-TOF-MS results: molecular ion peaks: 548.80 elemental analysis results: theoretical value: c,87.64; h,3.31; n,5.11 (%); experimental values: c,87.70; h,3.35; n,5.05 (%).
Synthetic example 48:
Figure BDA0003730919010000552
synthesis of Compound N-400-1
Figure BDA0003730919010000553
This example is essentially the same as the synthesis of compound N-366-1, except that: in this case, an equivalent amount of boron ester was replaced. N-400-1 (2.5 g) was obtained as a white solid.
Synthesis of Compound N-400-2
Figure BDA0003730919010000554
This example is essentially the same as the synthesis of compound N-366-1, and the specific procedure is as follows: 1-bromo-8- (3-bromo-5-cyanobenzene) naphthalene (1.90g, 5.00mmol), N-400-1 (2.49g, 5.00mmol), tetratriphenylphosphine palladium (0.18g, 0.15mmol) and potassium carbonate (1.73g, 12.50mmol) were sequentially added to a 100mL double-necked bottle. Under a nitrogen atmosphere, 50mL of tetrahydrofuran and 12mL of water were added, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 100mL of ethyl acetate are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 3:2) as eluent to give N-400-2 (1.5 g) as a yellow solid.
Synthesis of Compound N-400-3
Figure BDA0003730919010000561
This example is essentially the same as the synthesis of compound N-1, except that: in this case, N-1-1 is replaced by N-400-2 of equal mass. The aimed compound N-400-3 (1.1 g) was a yellow powder.
Synthesis of Compound N-400
Figure BDA0003730919010000562
This example is essentially the same as the synthesis of compound N-366, except that: in this example, N-366-1 is replaced by N-400-3. The target compound N-400 (0.19g, 16% yield, 96% purity by HPLC) was a red solid. MALDI-TOF-MS results: molecular ion peaks: 551.17 elemental analysis results: theoretical values are as follows: c,87.13; h,3.29; n,7.62 (%); experimental values: c,87.20; h,3.25; n,7.60 (%).
Synthetic example 49:
Figure BDA0003730919010000563
synthesis of Compound N-402-1
Figure BDA0003730919010000564
Diphenylamine (3.34g, 20.00mmol), 2,2' -dibromo-3 ',6' -dichloro-3,3 "-difluoro-1,1 ':4',1" -terphenyl (4.90g, 10.00mmol) and cesium carbonate (16.3g, 50.00mmol) were added sequentially to a 250mL two-neck flask. Under a nitrogen atmosphere, 100mL of N, N-dimethylformamide was added, and the reaction was stopped after 24 hours at 140 ℃. Cooled to room temperature, added to 500mL of water, filtered to collect the residue, and recrystallized from methylene chloride and methanol to give N-402-1 (4.1 g) as a white solid.
Synthesis of Compound N-402-2
Figure BDA0003730919010000571
This example is essentially the same as the synthesis of compound N-366-1, except that: in this case, equal amounts of bromide need to be replaced. The titled compound N-402-2 (2.6 g) was a pale yellow solid.
Synthesis of Compound N-402
Figure BDA0003730919010000572
This example is essentially the same as the synthesis of compound N-366 except that: in this example, N-366-1 is replaced by N-402-2. The target compound N-402 (0.28g, 18% yield, 96% purity by HPLC analysis) was a red solid. MALDI-TOF-MS results: molecular ion peaks: 832.28 elemental analysis results: theoretical value: c,89.44; h,4.60; n,3.36 (%); experimental values: c,89.49; h,4.53; n,3.34 (%).
Synthetic example 50:
Figure BDA0003730919010000573
synthesis of Compound N-412-1
Figure BDA0003730919010000574
This example is essentially the same as the synthesis of compound N-366-1, except that: in this case, equivalent amounts of halide and boron ester were replaced. White powder N-412-1 (2.9 g) was obtained.
Synthesis of Compound N-412
Figure BDA0003730919010000581
This example is essentially the same as the synthesis of compound N-366, except that: in this example, N-366-1 is replaced with N-412-1. The title compound N-412 (0.14g, 11% yield, 93% purity by HPLC) was an orange solid. MALDI-TOF-MS results: molecular ion peaks: 646.24 elemental analysis results: theoretical values are as follows: c,92.91; h,3.74 (%); experimental values: c,92.88; h,3.74 (%).
Synthetic example 51:
Figure BDA0003730919010000582
synthesis of Compound N-415-1
Figure BDA0003730919010000583
This example is essentially the same as the synthesis of compound N-366-1, except that: in this case, equal amounts of boron ester and halide are replaced. The titled compound N-415-1 (3.3 g) was a pale yellow powder.
Synthesis of Compound N-415-2
Figure BDA0003730919010000591
This example is essentially the same as the synthesis of compound N-1, except that: in this example, N-1-1 is replaced by N-415-1 of equal mass. The aimed compound N-415-2 (2.0 g) was an orange powder.
Synthesis of Compound N-415
Figure BDA0003730919010000592
This example is essentially the same as the synthesis of compound N-366, except that: in this example, N-366-1 is replaced by N-415-2. The title compound N-415 (0.48g, 29% yield, 97% purity by HPLC) was a black solid. MALDI-TOF-MS results: molecular ion peaks: 649.18 elemental analysis results: theoretical values are as follows: c,92.46; h,3.72; n,2.16 (%); experimental values: c,92.41; h,3.69; n,2.20 (%).
Synthesis example 52:
Figure BDA0003730919010000593
synthesis of Compound N-418
Figure BDA0003730919010000594
A25 mL two-necked flask was charged with N-48-1 (0.39g, 0.50mmol), 2,4,6-trimethylphenylboronic acid (0.18g, 1.10mmol), tetratriphenylphosphine palladium (17mg, 0.015mmol), and potassium carbonate (0.17g, 1.25mmol) in that order. Under a nitrogen atmosphere, 4mL of tetrahydrofuran and 1mL of water were added, and the reaction was stopped after 24 hours at 85 ℃. Cooled to room temperature, 200mL of ethyl acetate are added and extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate and the organic solvent was removed under reduced pressure. Column chromatography purification was performed using petroleum ether and dichloromethane (v/v = 1:1) as eluents to give the target compound N-418 (0.28g, 76% yield, 98% purity by HPLC) as a black solid. MALDI-TOF-MS results: molecular ion peaks: 740.35 elemental analysis results: theoretical values are as follows: c,90.78; h,5.44; n,3.78 (%); experimental values: c,90.73; h,5.47; n,3.79 (%).
The technical effects and advantages of the present invention are shown and demonstrated below by testing practical use properties by specifically applying the compounds of the present invention to organic electroluminescent devices.
Specifically, the preparation method of the organic electroluminescent device in the embodiment of the invention comprises the following steps:
1. the anode material coated glass plate was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
2. placing the glass plate with the anode in a vacuum chamber, and vacuumizing to 1 × 10 -5 ～9×10 -3 Pa, forming a hole injection layer by vacuum evaporation of a hole injection material on the anode layer film at a rate of0.1-0.5nm/s；
3. Vacuum evaporating hole transport material on the hole injection layer to form a hole transport layer with an evaporation rate of 0.1-0.5nm/s,
4. vacuum evaporating an electron barrier layer on the hole transport layer, wherein the evaporation rate is 0.1-0.5nm/s;
5. and vacuum evaporating the organic light-emitting layer of the device on the electron blocking layer, wherein the material of the organic light-emitting layer can be single-component or multi-component. The multi-component composition may include a host material, a sensitizer, a dye, or the like, or may be any combination thereof. Regulating the evaporation rate of the main material, the evaporation rate of the sensitizer material and the evaporation rate of the dye by using a multi-source co-evaporation method to enable the dye to reach a preset doping proportion;
6. vacuum evaporating a hole blocking layer on the organic light-emitting layer, wherein the evaporation rate is 0.1-0.5nm/s;
7. forming an electron transport layer on the hole barrier layer by vacuum evaporation of an electron transport material of the device, wherein the evaporation rate is 0.1-0.5nm/s;
8. LiF is evaporated on the electron transport layer in vacuum at a speed of 0.1-0.5nm/s to serve as an electron injection layer, and an Al layer is evaporated on the electron transport layer in vacuum at a speed of 0.5-1nm/s to serve as a cathode of the device.
The organic electroluminescent device according to the invention is further described below by means of specific examples.
Device example 1
The structure of the organic electroluminescent device prepared in this example is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:2wt％N-1(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
wherein the anode material is ITO; the hole injection layer is made of HI, the total thickness is generally 5-30nm, and the thickness is 10nm in the embodiment; the hole transport layer is made of HT, and the total thickness is generally 5-500nm, in this embodiment 30nm; host is a main body material with wide band gap of an organic light-emitting layer, the compound N-1 is dye and the doping concentration is 2wt%, the thickness of the organic light-emitting layer is generally 1-200nm, in this embodiment 30nm; the material of the electron transport layer is ET, the thickness is generally 5-300nm, in this embodiment 30nm; the electron injection layer and the cathode material are selected from LiF (0.5 nm) and metallic aluminum (150 nm).
A DC voltage was applied to the organic electroluminescent element D1 prepared in this example, and 10cd/m was measured 2 The characteristics in light emission were such that red light emission (drive voltage of 2.6V) having a wavelength of 605nm, a half-peak width of 32nm, CIE color coordinates (x, y) = (0.67,0.22), and an external quantum efficiency EQE of 4.2% was obtained.
Device example 2
The same preparation method as that of the device example 1 except that the wide band gap type Host material used in the light emitting layer was replaced with the TADF type Host TD1, the specific device structure was as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD1:2wt％N-1(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D2 prepared in this example are as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that red light emission (driving voltage of 2.5V) having a wavelength of 604nm, a half-peak width of 32nm, CIE color coordinates (x, y) = (0.66,0.23), and an external quantum efficiency EQE of 24.1% was obtained.
Device example 3
The same procedure as in device example 1 was followed except that the dye used in the light-emitting layer was replaced with N-6 from N-1.
The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:2wt％N-6(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D3 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 Orange emission (driving voltage of 2.7V) having a wavelength of 575nm, a half-peak width of 32nm, CIE color coordinates (x, y) = (0.53,0.44), and an external quantum efficiency EQE of 4.7% was obtained as characteristics in light emission.
Device example 4
The same preparation method as that of device example 1 was followed except that the wide band gap type Host material Host in the light-emitting layer was replaced with a TADF type Host TD1 and the dye was replaced with N-1 to N-6. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD1:2wt％N-6(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D4 prepared in this example are as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that orange light emission (driving voltage of 2.7V) having a wavelength of 576nm, a half-peak width of 32nm, CIE color coordinates (x, y) = (0.54,0.43), and external quantum efficiency EQE of 29.3% was obtained.
Device example 5
The same procedure as in device example 1 was followed except that the dye in the light-emitting layer was replaced with N-11 from N-1. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:2wt％N-11(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D5 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that green emission (drive voltage of 2.6V) having a wavelength of 535nm, a half-peak width of 29nm, CIE color coordinates (x, y) = (0.27,0.67), and an external quantum efficiency EQE of 4.2% was obtained.
Device example 6
The same preparation method as that of device example 1 was used except that the wide band gap type Host material in the light-emitting layer was replaced with TADF type Host TD1 and the dye was replaced with N-1 to N-11. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD1:2wt％N-11(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D6 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that green emission (driving voltage of 2.5V) having a wavelength of 532nm, a peak width at half maximum of 28nm, CIE color coordinates (x, y) = (0.25,0.70), and external quantum efficiency EQE of 24.1% was obtained.
Device example 7
The same procedure as in device example 1 was conducted except that the dye in the light-emitting layer was replaced with N-158 from N-1. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:2wt％N-158(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D7 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that red light emission (drive voltage of 2.6V) having a wavelength of 615nm, a half-peak width of 34nm, CIE color coordinates (x, y) = (0.68,0.21), and an external quantum efficiency EQE of 4.5% was obtained.
Device example 8
The same preparation method as that of device example 1 was used except that the wide band gap type Host material in the light-emitting layer was replaced with TADF type Host TD1 and the dye was replaced with N-1 to N-158. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD1:2wt％N-158(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D8 prepared in this example are as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that red light emission (drive voltage of 2.5V) having a wavelength of 616nm, a half-peak width of 34nm, CIE color coordinates (x, y) = (0.68,0.21), and external quantum efficiency EQE of 27.3% was obtained.
Device example 9
The same procedure as in device example 1 was conducted except that the dye in the light-emitting layer was replaced with N-172 from N-1. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:2wt％N-172(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D9 prepared in this example are as follows: applying a DC voltage, measuring 10cd/m 2 The characteristics in light emission were such that red light emission (drive voltage of 2.3V) having a wavelength of 606nm, a half-peak width of 35nm, CIE color coordinates (x, y) = (0.71,0.28), and external quantum efficiency EQE of 5.6% was obtained.
Device example 10
The same preparation method as that of device example 1 was followed except that the wide band gap type Host material Host in the light-emitting layer was replaced with a TADF type Host TD1 and the dye was replaced with N-1 to N-172. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD1:2wt％N-172(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D10 prepared in this example were as follows: applying a DC voltage, measuring 10cd/m 2 The characteristics in light emission were such that red light emission (drive voltage of 2.2V) having a wavelength of 606nm, a half-peak width of 34nm, CIE color coordinates (x, y) = (0.71,0.29), and external quantum efficiency EQE of 18.4% was obtained.
Device example 11
The same procedure as in device example 1 was followed except that the dye in the light-emitting layer was replaced with N-201 from N-1. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:2wt％N-201(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D11 prepared in this example were as follows: applying a DC voltage, measuring 10cd/m 2 The characteristics in light emission were such that red light emission (drive voltage of 2.7V) having a wavelength of 611nm, a half-peak width of 37nm, CIE color coordinates (x, y) = (0.68,0.30), and an external quantum efficiency EQE of 4.8% was obtained.
Device example 12
The same preparation method as that of device example 1 was used except that the wide band gap type Host material in the light-emitting layer was replaced with TADF type Host TD1 and the dye was replaced with N-1 to N-201. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD1:2wt％N-201(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D12 prepared in this example were as follows: applying a DC voltage, measuring 10cd/m 2 The characteristics in light emission were such that red light emission (drive voltage of 2.6V) having a wavelength of 611nm, a half-peak width of 39nm, CIE color coordinates (x, y) = (0.69,0.30), and an external quantum efficiency EQE of 20.4% was obtained.
Device example 13
The same procedure as in device example 1 was followed except that the dye in the light-emitting layer was replaced with N-211 instead of N-1. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:2wt％N-211(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D13 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that yellow light emission (drive voltage 2.8V) having a wavelength of 548nm, a half-peak width of 29nm, CIE color coordinates (x, y) = (0.39,0.52), and an external quantum efficiency EQE of 3.6% was obtained.
Device example 14
The same preparation method as that of device example 1 was used except that the wide band gap type Host material in the light-emitting layer was replaced with TADF type Host TD1 and the dye was replaced with N-1 to N-211. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD1:2wt％N-211(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D14 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that yellow light emission (drive voltage 2.8V) having a wavelength of 548nm, a half-peak width of 29nm, CIE color coordinates (x, y) = (0.39,0.52), and an external quantum efficiency EQE of 18.4% was obtained.
Device example 15
The same procedure as in device example 1 was conducted except that the dye in the light-emitting layer was replaced with N-248 from N-1. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:2wt％N-248(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D15 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission include a wavelength of 562nm, a half-width of 38nm, CIE color coordinates (x, y) = (0.51,0.44), and an external quantum efficiency EQE of 26% orange luminescence (drive voltage 2.6V).
Device example 16
The same preparation method as that of device example 1 was used except that the wide band gap type Host material in the light-emitting layer was replaced with TADF type Host TD1 and the dye was replaced with N-1 to N-248. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD1:2wt％N-248(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D16 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 Orange emission (driving voltage of 2.6V) having a wavelength of 562nm, a half-peak width of 38nm, CIE color coordinates (x, y) = (0.51,0.44), and an external quantum efficiency EQE of 23.1% was obtained as characteristics in light emission.
Device example 17
The same procedure as in device example 1 was conducted except that the dye in the light-emitting layer was replaced with N-299 from N-1. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:2wt％N-299(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D17 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that yellow light emission (drive voltage of 2.5V) having a wavelength of 552nm, a half-peak width of 35nm, CIE color coordinates (x, y) = (0.45,0.51), and external quantum efficiency EQE of 3.2% was obtained.
Device example 18
The same preparation method as that of device example 1 was used except that the wide band gap type Host material Host in the light-emitting layer was replaced with a TADF type Host TD1 and the dye was replaced with N-1 to N-299. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD1:2wt％N-299(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D18 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 In the light emissionIn this case, yellow emission (drive voltage of 2.5V) having a wavelength of 553nm, a half-peak width of 35nm, CIE color coordinates (x, y) = (0.45,0.51), and an external quantum efficiency EQE of 20.7% was obtained.
Device example 19
The same procedure as in device example 1 was followed except that the dye in the light-emitting layer was replaced with N-309 from N-1. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:2wt％N-309(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D19 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that red light emission (drive voltage of 2.6V) having a wavelength of 625nm, a half-peak width of 35nm, CIE color coordinates (x, y) = (0.70,0.29), and external quantum efficiency EQE of 3.9% was obtained.
Device example 20
The same preparation method as that of device example 1 was used except that the wide band gap type Host material in the light-emitting layer was replaced with TADF type Host TD1 and the dye was replaced with N-1 to N-309. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD1:2wt％N-309(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D20 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that red light emission (drive voltage of 2.5V) having a wavelength of 626nm, a half-peak width of 35nm, CIE color coordinates (x, y) = (0.70,0.29), and external quantum efficiency EQE of 22.7% was obtained.
Device example 21
The same procedure as in device example 1 was followed except that the dye in the light-emitting layer was replaced with N-336 from N-1. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:2wt％N-366(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D21 prepared in this example were as follows: applying straightFlow voltage, measurement of 10cd/m 2 The characteristics in light emission were such that red light emission (drive voltage of 2.6V) having a wavelength of 608nm, a peak width at half maximum of 33nm, CIE color coordinates (x, y) = (0.65,0.35), and an external quantum efficiency EQE of 5.2% was obtained.
Device example 22
The same preparation method as that of device example 1 was used except that the wide band gap type Host material in the light-emitting layer was replaced with TADF type Host TD1 and the dye was replaced with N-1 to N-336. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD1:2wt％N-336(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D22 prepared in this example were as follows: applying a DC voltage, measuring 10cd/m 2 The characteristics in light emission were such that red light emission (drive voltage of 2.5V) having a wavelength of 608nm, a half-peak width of 34nm, CIE color coordinates (x, y) = (0.65,0.35), and external quantum efficiency EQE of 18.4% was obtained.
Device example 23
The same procedure as in device example 1 was followed, except that the dye in the light-emitting layer was replaced with N-341 from N-1. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:2wt％N-341(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D23 prepared in this example were as follows: applying a DC voltage, measuring 10cd/m 2 The characteristics in light emission were such that orange light emission (drive voltage of 2.6V) having a wavelength of 579nm, a half-peak width of 24nm, CIE color coordinates (x, y) = (0.55,0.42), and an external quantum efficiency EQE of 4.7% was obtained.
Device example 24
The same preparation method as that of device example 1 was followed except that the wide band gap type Host material Host in the light-emitting layer was replaced with a TADF type Host TD1 and the dye was replaced with N-1 to N-341. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD1:2wt％N-341(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D24 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that orange light emission (drive voltage of 2.6V) having a wavelength of 580nm, a peak width at half maximum of 24nm, CIE color coordinates (x, y) = (0.56,0.41), and external quantum efficiency EQE of 27.4% was obtained.
Device example 25
The same procedure as in device example 1 was conducted except that the dye in the light-emitting layer was replaced with N-391 from N-1. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:2wt％N-391(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D25 prepared in this example were as follows: applying a DC voltage, measuring 10cd/m 2 The characteristics in light emission were such that red light emission (drive voltage of 2.6V) having a wavelength of 612nm, a half-peak width of 38nm, CIE color coordinates (x, y) = (0.66,0.33), and an external quantum efficiency EQE of 3.8% was obtained.
Device example 26
The same production method as that of device example 1 was used except that the wide band gap type Host material Host in the light-emitting layer was replaced with a TADF type Host TD1 and the dye was replaced with N-1 to N-391. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD1:2wt％N-391(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D26 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that red light emission (drive voltage of 2.5V) having a wavelength of 612nm, a half-peak width of 38nm, CIE color coordinates (x, y) = (0.66,0.33), and external quantum efficiency EQE of 23.1% was obtained.
Device example 27
The same procedure as in device example 1 was followed except that the dye in the light-emitting layer was replaced with N-393 from N-1. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:2wt％N-393(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D27 prepared in this example were as follows: applying a DC voltage, measuring 10cd/m 2 The characteristics in light emission were such that green emission (drive voltage of 2.6V) having a wavelength of 530nm, a peak width at half maximum of 27nm, CIE color coordinates (x, y) = (0.20,0.74), and an external quantum efficiency EQE of 2.6% was obtained.
Device example 28
The same preparation method as that of device example 1 was used except that the wide band gap type Host material Host in the light-emitting layer was replaced with TADF type Host TD2 and the dye was replaced with N-1 to N-393. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD2:2wt％N-393(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D28 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that green emission (driving voltage of 2.5V) having a wavelength of 530nm, a peak width at half maximum of 28nm, CIE color coordinates (x, y) = (0.21,0.75), and external quantum efficiency EQE of 23.7% was obtained.
Device example 29
The same procedure as in device example 1 was followed except that the dye in the light-emitting layer was replaced with N-405 from N-1. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:2wt％N-405(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D29 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that orange light emission (drive voltage of 2.8V) having a wavelength of 586nm, a half-peak width of 45nm, CIE color coordinates (x, y) = (0.58,0.41), and external quantum efficiency EQE of 5.3% was obtained.
Device example 30
The same preparation method as that of device example 1 was used except that the wide band gap type Host material Host in the light-emitting layer was replaced with a TADF type Host TD1 and the dye was replaced with N-1 to N-405. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD1:2wt％N-405(30nm)/HBL(10nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D30 prepared in this example were as follows: applying a DC voltage, measuring 10cd/m 2 The characteristics in light emission were such that orange light emission (drive voltage of 2.7V) having a wavelength of 586nm, a half-peak width of 46nm, CIE color coordinates (x, y) = (0.58,0.41), and external quantum efficiency EQE of 21.4% was obtained.
Comparative device example 1
The same preparation method as that of device example 1 was used except that the compound N-1 of the present invention used in the light-emitting layer was replaced with the compound TBRb of the prior art, and the specific device structure was as follows:
ITO/HI(10nm)/HT(40nm)/Host:2wt％TBRb(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device DD1 prepared in this example are as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were that yellow-orange light emission (drive voltage of 2.8V) having a wavelength of 569nm, a half-peak width of 74nm, CIE color coordinates (x, y) = (0.45,0.53), and an external quantum efficiency EQE of 3.5% was obtained.
Comparative device example 2
The same preparation method as that of device example 2 except that the compound N-1 of the present invention used in the light-emitting layer was replaced with the compound TBRb of the prior art, and a specific device structure was as follows:
ITO/HI(10nm)/HT(40nm)/TD1:2wt％TBRb(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device DD2 prepared in this example are as follows: applying a DC voltage, and measuring 10cd/m 2 The characteristics in light emission were such that yellow-orange light emission (drive voltage of 2.6V) having a wavelength of 570nm, a half-peak width of 77nm, CIE color coordinates (x, y) = (0.44,0.54), and an external quantum efficiency EQE of 14.7% was obtained.
Comparative device example 3
The same preparation method as that of device example 1 was followed except that the compound N-1 of the present invention used in the light-emitting layer was replaced with the compound DABNA-1 of the prior art, and the specific device structure was as follows:
ITO/HI(10nm)/HT(40nm)/Host:2wt％DABNA-1(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the performance results of the organic electroluminescent device DD3 prepared in this example are as follows: applying a DC voltage, and measuring 10cd/m 2 In the characteristics in light emission, blue light emission (driving voltage of 3.2V) having a wavelength of 470nm, a half-width of 30nm, CIE color coordinates (x, y) = (0.13,0.12), and an external quantum efficiency EQE of 4.1% was obtained.
Comparative device example 4
The same preparation method as in device example 2 was conducted except that the compound N-1 of the present invention used in the light-emitting layer was replaced with the compound DABNA-1 of the prior art, and the specific device structure was as follows:
ITO/HI(10nm)/HT(40nm)/TD2:2wt％DABNA-1(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device DD4 prepared in this example are as follows: applying a DC voltage, measuring 10cd/m 2 The characteristics in light emission were such that blue light emission (drive voltage of 3.2V) having a wavelength of 472nm, a half-peak width of 32nm, CIE color coordinates (x, y) = (0.13,0.12), and an external quantum efficiency EQE of 17.3% was obtained.
Comparative device example 5
The same preparation method as that of device example 1 was followed except that the compound N-1 of the present invention used in the light-emitting layer was replaced with the compound DM1 of the prior art, and the specific device structure was as follows:
ITO/HI(10nm)/HT(40nm)/Host:2wt％DM1(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device DD5 prepared in this example are as follows: applying a DC voltage, measuring 10cd/m 2 The characteristics in light emission were such that blue light emission (drive voltage of 3.2V) having a wavelength of 480nm, a half-peak width of 35nm, CIE color coordinates (x, y) = (0.15,0.20), and external quantum efficiency EQE of 3.1% was obtained.
Comparative device example 6
The same preparation method as that of device example 2 except that the compound N-1 of the present invention used in the light-emitting layer was replaced with the compound DM1 of the prior art, and a specific device structure was as follows:
ITO/HI(10nm)/HT(40nm)/TD2:2wt％DM1(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device DD6 prepared in this example are as follows: applying a DC voltage, and measuring 10cd/m 2 In the characteristics in light emission, blue light emission (driving voltage of 3.2V) having a wavelength of 482nm, a half-peak width of 35nm, CIE color coordinates (x, y) = (0.15,0.21), and an external quantum efficiency EQE of 14.4% was obtained.
The structural formulas of the various organic materials used in the above examples are as follows:
Figure BDA0003730919010000681
Figure BDA0003730919010000691
Figure BDA0003730919010000701
specific performance data of the organic electroluminescent devices D1 to D30 and the devices DD1, DD2, DD3, DD4, DD5, and DD6 prepared in the respective device examples described above are detailed in table 1 below.
Table 1:
Figure BDA0003730919010000702
Figure BDA0003730919010000711
Figure BDA0003730919010000721
as can be seen from the data in Table 1, compared with the compound TBRb, the compound DABNA-1 and the compound DM1 in the prior art, the compound of the invention belongs to a stable MR type narrow spectrum fluorescent dye. The classical orange fluorescent dye TBRb has higher fluorescence quantum yield, but the TBRb can hardly meet the requirement of BT2020 on color purity due to wider fluorescence emission spectrum. Compared with DABNA-1, the multiple resonance effect is realized by introducing boron nitrogen atoms for induction, and a narrow-emission fluorescence spectrum is obtained, but the DABNA-1 is sensitive to water and oxygen, has poor chemical stability, and has long delayed fluorescence lifetime which also influences the stability of the device. The compound DM1 serving as a traditional fluorescent dye also has a narrower fluorescence spectrum and a shorter fluorescence life, but the material has limited electron cloud distribution delocalization, a larger energy band and higher driving voltage, so that the material also faces the stability problem. In the invention, the conjugated expansion is carried out in a six-membered fusion mode on the basis of an indolocarbazole-like structure, the hybridization of a non-bond orbit and a pi orbit can be realized, and the multiple resonance effect and the exciton dynamics process are considered. Different from the traditional multiple resonance fluorescent dye, the dye utilizes the electronegativity difference of nitrogen/boron atoms and carbon atoms to realize the non-bond orbit characteristic, thereby inhibiting the spectrum broadening caused by the high-frequency vibration of molecules. In addition, the electronegativity difference between nitrogen/boron atoms and carbon atoms is moderate, so that the molecules have weaker charge transfer characteristics, have larger single triplet state energy levels and are beneficial to accelerating the exciton kinetic process. Because the bond energy of C-N and C-C is higher, the dye molecules also have better chemical stability and water-oxygen tolerance, and a multiple resonance type material system is greatly enriched. As can be seen from the above results, the electroluminescence spectrum of the example has a small half-peak width, confirming that it has an effective multiple resonance effect. In addition, compared with comparative examples DD4 and DD6, the thermally activated sensitized fluorescent device of the embodiment has smaller driving voltage, and the efficiency and the stability are obviously improved, so that the structure provided by the invention has great advantage in improving the device performance. The compound has good application prospect due to excellent efficiency, color purity and stability.
The organic electroluminescent compound and the application thereof provided by the present invention are described in detail above, and the principle and the embodiment of the present invention are illustrated herein by using specific examples, and the above description of the examples is only for helping to understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.

Claims (9)

1. An organic compound having a structure represented by the following formula (I):
Figure FDA0003730911000000011
in formula (I), the dotted line represents a single bond linkage or no linkage;
X 1 and X 2 Each independently is N or B;
ring A represents a benzene ring, a naphthalene ring or an anthracene ring;
ring B and ring C each independently represent a benzene ring, a naphthalene ring or an anthracene ring;
ring D and ring E each independently represent a C8-C60 fused aromatic hydrocarbon;
the R is A 、R B 、R C 、R D And R E Each independently represents a substituent group from a single substituent group to the maximum permissible number of substituents, R A 、R B 、R C 、R D And R E Each is independently selected from hydrogen, deuterium, halogen, carbonyl, carboxyl, nitro, cyano, amino, silicon base, substituted or unsubstituted chain alkyl of C1-C36, substituted or unsubstituted cycloalkyl of C3-C36, substituted or unsubstituted alkoxy of C1-C10, substituted or unsubstituted thioalkoxy of C1-C10, substituted or unsubstituted arylamino of C6-C30, and substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C60 monocyclic aryl or fused ring aryl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C5-C60 heteroaryl;
the R is A 、R B 、R C 、R D And R E Each of which is linked to the ring A, ring B, ring C, ring D and ring E via a single bond, or R A 、R B 、R C 、R D And R E Each fused to the linking ring A, ring B, ring C, ring D, and ring E;
when the above R is A 、R B 、R C 、R D And R E When the substituent exists, the substituent group is independently selected from one of deuterium, halogen, nitro, cyano, amino, carbonyl, carboxyl, chain alkyl of C1-C30, cycloalkyl of C3-C30, alkoxy of C1-C10, thioalkoxy of C1-C10, arylamino of C6-C30, heteroarylamino of C3-C30, aryl of C6-C60, aryloxy of C6-C60 and heteroaryl of C5-C60.
2. The organic compound according to claim 1, having a structure represented by any one of the following formulae (1), (2) or (3):
Figure FDA0003730911000000012
in formulae (1) to (3), ring d 1 Ring d 2 Ring e 1 And ring e 2 Each independently represents a C6-C30 aromatic ring;
said X 1 、X 2 Ring A, ring B, ring C, R A 、R B 、R C 、R D And R E Are as defined in formula (I);
the R is B 、R C 、R D And R E Each of which is linked to the attached ring structure by a single bond or fused.
3. The organic compound according to claim 1 or 2, wherein ring a represents a benzene ring, a naphthalene ring or an anthracene ring, and ring B and ring C are both benzene rings;
or, the ring A, the ring B and the ring C are all benzene rings.
4. The organic compound according to claim 1 or 2, having a structure represented by any one of the following formulae (4), (5), or (6):
Figure FDA0003730911000000021
in formulae (4) to (6), the X 1 、X 2 、R A 、R B 、R C 、R D And R E Are as defined in formula (I);
the R is B 、R C 、R D And R E Each of which is linked to the attached ring structure by a single bond or fused.
5. The organic compound of any one of claims 1,2, or 4, said X 1 And X 2 And are simultaneously N atoms;
or, the X 1 And X 2 And at the same time is a B atom.
6. The organic compound of any one of claims 1,2, or 4, wherein R A 、R B 、R C 、R D And R E Each independently selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, bornyl, perylenyl, fluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenylA phenyl group, a quaterphenyl group, a fluorenyl group, a spirobifluorenyl group, a phenanthrenyl group, a pyrenyl group, a tetrahydropyrenyl group, a cis-or trans-indenofluorenyl group, a trimeric indenyl group, an isotridecyl group, a spirotrimeric indenyl group, a spiroisotridecyl group, a furyl group, a benzofuryl group, an isobenzofuryl group, a dibenzofuryl group, a thienyl group, a benzothienyl group, an isobenzothienyl group, a dibenzothienyl group, a pyrrolyl group, an isoindolyl group, a carbazolyl group, an indenocarbazolyl group pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl phenanthrenyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazanthronyl, 2,7-diazenylyl, 2,3-diazenylyl, 1,6-diazenylyl, 1,8-diazenylyl, 4,5-diazenylyl, 4,5,9,10-tetraazazolyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 3826 xzft 3926-oxadiazolyl, 3928 zxft 348625-5427-oxadiazolyl, 74zzft 8678-74zzft 8678, oxadiazolyl, 74xzft 3926-74xzft 3927-7439-diazenyl, 74xzft 8678-74xzft 8678, and oxadiazolyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 9,9-dimethylazinyl, diarylamine, triarylamine, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, tetrahydropyrrole, piperidine, methoxy, silicon, or a combination of two substituents selected from the above;
preferably, said R is A 、R B 、R C 、R D And R E Each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl and goldOne of an alkyl group, a fluorine group, a trifluoromethyl group, a phenyl group, a trimethylphenyl group, a naphthyl group, an anthracenyl group, a furyl group, a tetrahydrofuryl group, a pyrrolyl group, a tetrahydropyrrolyl group, a thienyl group, a carbazolyl group, a triazinyl group, a pyridyl group, a quinolyl group, an acridinyl group, a cyano group, a methoxy group, a silicon group, a dimethylamino group, a triarylamine group, a fluorenyl group, a dibenzofuryl group, a dibenzothienyl group, or a combination of two substituent groups.
7. The organic compound according to claim 1, selected from the following compounds of specific structure:
Figure FDA0003730911000000041
Figure FDA0003730911000000051
Figure FDA0003730911000000061
Figure FDA0003730911000000071
Figure FDA0003730911000000081
Figure FDA0003730911000000091
Figure FDA0003730911000000101
Figure FDA0003730911000000111
Figure FDA0003730911000000121
Figure FDA0003730911000000131
Figure FDA0003730911000000141
Figure FDA0003730911000000151
8. use of the compound of any one of claims 1 to 7 as a functional material in an organic electronic device comprising an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet-type scanner or electronic paper;
further, the compound is applied to be used as a luminescent layer material in an organic electroluminescent device, and particularly used as a luminescent material in a luminescent layer.
9. An organic electroluminescent device comprising a first electrode, a second electrode and one or more light-emitting functional layers interposed between the first electrode and the second electrode, wherein the light-emitting functional layers contain therein a compound according to any one of claims 1 to 7;
furthermore, the light-emitting functional layer comprises a hole transport region, a light-emitting layer and an electron transport region, wherein the hole transport region is formed on the anode layer, the cathode layer is formed on the electron transport region, and the light-emitting layer is arranged between the hole transport region and the electron transport region; wherein the light-emitting layer contains the compound according to any one of claims 1 to 7.
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