CN111018847A

CN111018847A - Nitrogen-containing compound, electronic component, and electronic device

Info

Publication number: CN111018847A
Application number: CN201911054880.XA
Authority: CN
Inventors: 马天天; 杨敏; 南朋
Original assignee: Shaanxi Lighte Optoelectronics Material Co Ltd
Current assignee: Shaanxi Lighte Optoelectronics Material Co Ltd
Priority date: 2019-10-31
Filing date: 2019-10-31
Publication date: 2020-04-17
Also published as: KR102363659B1; WO2021083030A1; CN111393420A; KR20210129215A; CN111393420B

Abstract

The disclosure provides a nitrogen-containing compound, an electronic element and an electronic device, and relates to the technical field of organic materials. The nitrogen-containing compound is shown as a formula I, wherein X is selected from oxygen or sulfur; r is selected from heterocycloalkyl and heteroaryl; l is selected from single bond, arylene, heteroarylene; the substituent of R is selected from deuterium, nitro, hydroxyl, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl and heteroCycloalkyl, alkoxy, arylsilyl, or alkylsilyl; the substituent of L is selected from deuterium, nitro, hydroxyl, alkyl, cycloalkyl, alkenyl, alkynyl, heterocycloalkyl, alkoxy, alkylsilyl, arylsilyl, aryloxy, arylthio. The nitrogen-containing compounds of the present disclosure can reduce the operating voltage of electronic components, improve device efficiency, and extend device lifetime.

Description

Nitrogen-containing compound, electronic component, and electronic device

Technical Field

The present disclosure relates to the field of organic materials, and in particular, to a nitrogen-containing compound, an electronic component, and an electronic device.

Background

In recent years, with the development of semiconductor technology, electronic components have been widely used, for example: organic electroluminescent devices (OLEDs) are gradually coming into the field of vision of people as a new generation of display devices. A common organic electroluminescent device is composed of an anode, a cathode, and an organic layer interposed between the cathode and the anode. When voltage is applied to the cathode and the anode, the two electrodes generate an electric field, electrons on the cathode side and holes on the anode side move to the light-emitting layer simultaneously under the action of the electric field, the electrons and the holes combine to form excitons in the light-emitting layer, the excitons are in an excited state and release energy outwards, and light is emitted outwards in the process of changing from the excited state to a ground state.

The existing organic electroluminescent device mainly comprises a hole transport layer, a luminescent layer and an electron transport layer, but because the transport performance of current carriers among the layers is poor, the working voltage of the device is increased, the luminous efficiency is reduced, the service life is shortened, and the performance of the device is reduced.

This has also been investigated in the prior art literature, for example: patent documents KR 1020170097242; patent document KR1020170161944 and patent document KR 1020170048045.

It is to be noted that the information disclosed in the above background section is only for enhancement of understanding of the background of the present disclosure, and thus may include information that does not constitute prior art known to those of ordinary skill in the art.

Disclosure of Invention

The present disclosure is directed to overcoming the above-mentioned deficiencies in the prior art, and providing a nitrogen-containing compound, an electronic component and an electronic device, which can reduce the operating voltage, improve the light-emitting efficiency, and prolong the lifetime of the device.

According to one aspect of the present disclosure, there is provided a nitrogen-containing compound, wherein the structure general formula of the nitrogen-containing compound is shown as formula I:

wherein X is oxygen or sulfur;

r is selected from: a substituted or unsubstituted heterocycloalkyl group having 1 to 10 ring-forming carbon atoms, a substituted or unsubstituted heteroaryl group having 4 to 20 ring-forming carbon atoms;

l is selected from: a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylene group having 1 to 30 carbon atoms;

the substituents of R are selected from: deuterium, nitro, hydroxyl, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycloalkyl, alkoxy, arylsilyl, alkylsilyl;

the substituents of the L are selected from: deuterium, nitro, hydroxyl, alkyl, cycloalkyl, alkenyl, alkynyl, heterocycloalkyl, alkoxy, arylsilyl, alkylsilyl, aryloxy, arylthio.

According to one aspect of the present disclosure, there is provided an electronic component including an anode and a cathode disposed opposite to each other, and a functional layer disposed between the anode and the cathode;

the functional layer comprises a compound according to any one of the above.

According to an aspect of the present disclosure, there is provided an electronic device including the electronic element of any one of the above.

The disclosed nitrogen-containing compound, electronic element and electronic device combine the substituent group with nitrogen heterocycle to the commonly used electron transport group 2, 4-diphenyl-1, 3, 5-triazine through 2, 4-disubstituted dibenzofuran (or dibenzothiophene) group, on one hand, the molecule has electron-deficient large conjugated plane structure formed by directly combining triazine and 4-position of dibenzofuran (or dibenzothiophene), which is helpful to improve electron transport rate and further improve device efficiency; on the other hand, nitrogen heterocycles can be introduced into the structure that the 2 nd position of dibenzofuran (or dibenzothiophene) and triazine are meta (nonconjugated) or para, so that the electron injection capability of the material can be effectively enhanced, and the efficiency and the service life of the device can be further improved.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present disclosure and together with the description, serve to explain the principles of the disclosure. It is to be understood that the drawings in the following description are merely exemplary of the disclosure, and that other drawings may be derived from those drawings by one of ordinary skill in the art without the exercise of inventive faculty.

Fig. 1 is a schematic structural view of an organic electroluminescent device according to an embodiment of the present disclosure.

Fig. 2 is a schematic structural diagram of a solar cell according to an embodiment of the present disclosure.

Fig. 3 is a schematic view of an electronic device according to an embodiment of the disclosure.

In the figure: 1. an anode; 2. a hole injection layer; 3. a functional layer; 31. a hole transport layer; 32. an electron blocking layer; 33. a light emitting layer; 34. an electron transport layer; 4. an electron injection layer; 5. a cathode; 100 a substrate; 200. an anode; 300. a functional layer; 301. a hole transport layer; 302. a photosensitive active layer; 303. an electron transport layer; 400. a cathode; 500. and (6) a screen.

Detailed Description

Example embodiments will now be described more fully with reference to the accompanying drawings. Example embodiments may, however, be embodied in many different forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of example embodiments to those skilled in the art. The described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided to give a thorough understanding of embodiments of the disclosure.

The terms "the" and "said" are used to indicate the presence of one or more elements/components/etc.; the terms "comprising" and "having" are intended to be inclusive and mean that there may be additional elements/components/etc. other than the listed elements/components/etc.

The disclosed embodiment provides a nitrogen-containing compound, which has a structural general formula shown in formula I:

the compound of the formula I is shown in the specification,

wherein X is oxygen or sulfur;

the substituents for L are selected from: deuterium, nitro, hydroxyl, alkyl, cycloalkyl, alkenyl, alkynyl, heterocycloalkyl, alkoxy, arylsilyl, alkylsilyl, aryloxy, arylthio.

The disclosed nitrogen-containing compound combines a substituent group with nitrogen heterocycle onto a commonly used electron transport group 2, 4-diphenyl-1, 3, 5-triazine through a 2, 4-disubstituted dibenzofuran (or dibenzothiophene) group, on one hand, the molecule has an electron-deficient large conjugated plane structure formed by directly combining the triazine and the 4 th site of the dibenzofuran (or dibenzothiophene), which is beneficial to improving the electron transport rate and further improving the device efficiency; on the other hand, nitrogen heterocycles can be introduced into the structure that the 2 nd position of dibenzofuran (or dibenzothiophene) and triazine are meta (nonconjugated) or para, so that the electron injection capability of the material can be effectively enhanced, and the efficiency and the service life of the device can be further improved.

The following describes in detail the portions of the nitrogen-containing compounds of the embodiments of the present disclosure:

the general structural formula of the nitrogen-containing compound is shown as formula I:

wherein, X can be selected from oxygen or sulfur;

l can be selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroarylene group having 1 to 30 carbon atoms. Of course, L may be selected from other groups, and is not particularly limited herein. For example, L may be selected from one or more of a single bond, phenylene, dimethylfluorenyl, biphenylene, naphthylene, or terphenylene, and is not particularly limited thereto. In one embodiment, L is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, which may have 6, 8, 10, 12, or 15 carbon atoms. In another embodiment, L is selected from a substituted or unsubstituted heteroarylene group of 5 to 12 carbon atoms, for example, 5, 6, 8, 10, or 12 carbon atoms. Of course, the number of carbon atoms may be other, and is not listed here.

Substituents for L may be selected from: deuterium, nitro, hydroxyl, alkyl, cycloalkyl, alkenyl, alkynyl, heterocycloalkyl, alkoxy, arylsilyl, alkylsilyl, aryloxy, arylthio.

In one embodiment, L is selected from the group formed by:

wherein may represent the above groups for use in combination with formula I

Group bonding;

may represent the above groups for binding to the R group in formula I.

R can be selected from: a substituted or unsubstituted heterocycloalkyl group having 1 to 10 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 20 ring-forming carbon atoms.

Preferably, R is selected from substituted or unsubstituted heterocycloalkyl having 3 to 5 ring-forming carbon atoms. For example, the number of carbon atoms may be 3,4 or 5, and the number of carbon atoms forming the ring may be other, and is not particularly limited.

Preferably, R is selected from substituted or unsubstituted heteroaryl with 5-15 ring carbon atoms. For example, the number of carbon atoms may be 5, 8, 9, 10, 12, 13 or 15, although the number of carbon atoms may be other, which is not listed here.

For example, R is selected from: thienyl, furyl, pyrrolyl, imidazolyl, oxazolyl, triazolyl, pyridyl, bipyridyl, acridinyl, pyridazinyl, quinolyl, quinazolinyl, benzimidazolyl, benzothienyl, benzocarbazolyl, benzoxazolyl, phenanthrolinyl, isoxazolyl, phenothiazinyl, benzoquinolyl, benzoquinoxalinyl, pyridoquinolyl, naphthyridinyl, and the like.

Preferably, R may be selected from the following substituted or unsubstituted groups: pyridyl, bipyridyl, quinolyl, quinoxalinyl, quinazolinyl, naphthyridinyl, benzoquinolyl, phenanthrolinyl, benzoquinoxalinyl, pyridoquinolyl.

The substituents for R may be selected from: deuterium, nitro, hydroxyl, alkyl, cycloalkyl, alkenyl, alkynyl, heterocycloalkyl, alkoxy, arylsilyl, alkylsilyl.

Preferably, the substituents for R may be selected from: an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a heterocycloalkyl group having 2 to 10 carbon atoms.

In the embodiments of the present disclosure, the number of carbon atoms of L means all the number of carbon atoms (including substituents) of L. For example: the substituted arylene group having 12 carbon atoms is such that all of the carbon atoms of the arylene group and the substituents thereon are 12.

The number of ring-forming carbon atoms referred to by R in the present disclosure refers to the number of carbon atoms (including no substituent) for ring formation of R, for example,

the group is substituted pyridyl and belongs to substituted heteroaryl with the cyclic carbon number of 5.

"cycloalkyl" refers to a saturated hydrocarbon group containing one or more rings in the molecular structure.

"heterocycloalkyl" refers to a group in which at least one carbon atom of the cycloalkyl group is replaced by a heteroatom N, O, P, S or Si. The number of carbon atoms for ring formation in the heterocycloalkyl group may be 1 to 10, which may be 3,4, 5 or 10. Of course, other numbers are possible, and are not particularly limited herein.

"aryl" means an optional functional group or substituent derived from an aromatic hydrocarbon ring, including monocyclic aryl and polycyclic aryl groups, in other words, the aryl groups can be monocyclic aryl, fused ring aryl, two or more monocyclic aryl groups joined by carbon-carbon bond conjugates, monocyclic aryl and fused ring aryl groups joined by carbon-carbon bond conjugates, two or more fused ring aryl groups joined by carbon-carbon bond conjugates. That is, two or more aromatic groups conjugated through a carbon-carbon bond may also be considered as an aryl group in the present application. Wherein the aryl group does not contain a heteroatom such as B, N, O, S or P. The number of carbon atoms in the aryl group may be 6 to 30, and it may be 6, 10, 12, 14, 20, 25 or 30, and of course, other numbers may be used, and is not particularly limited herein. By way of example, the aryl group may be: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, fluorenyl, dimethylfluorenyl, 9-diphenylfluorenyl, spirobifluorenyl, phenanthrenyl, and the like.

In this application, substituted aryl refers to an aryl group in which one or more hydrogen atoms are replaced with another group. For example, at least one hydrogen atom is substituted with deuterium atoms, hydroxyl groups, nitro groups, amino groups, branched alkyl groups, linear alkyl groups, cycloalkyl groups, alkoxy groups, alkylamino groups, or other groups. It is understood that a substituted aryl group having 18 carbon atoms refers to an aryl group and the total number of carbon atoms in the substituents on the aryl group being 18. For example, 9, 9-diphenylfluorenyl has 25 carbon atoms.

"heteroaryl" refers to a group in which at least one carbon atom of the aryl group is replaced with a heteroatom N, O, P, S or Si. The number of carbon atoms in the heteroaryl group may be 1 to 30, and it may be 2, 5, 12, 13, 14, 20, 25 or 30, and of course, other numbers may be used, and is not particularly limited herein. Where the heteroaryl group is monocyclic, the heteroaryl group does not contain more than 2 nitrogen atoms.

Preferably, the number of ring-forming carbon atoms of the heteroaryl group is 5 to 15. For example, heteroaryl groups may be: pyridyl, bipyridyl, thienyl, furyl, pyrrolyl, imidazolyl, oxazolyl, triazolyl, pyridyl, bipyridyl, acridinyl, pyridazinyl, quinolyl, quinazolinyl, benzimidazolyl, benzothienyl, benzocarbazolyl, benzoxazolyl, phenanthrolinyl, isoxazolyl, phenothiazinyl, benzoquinolyl, benzoquinoxalinyl, pyridoquinolyl, naphthyridinyl, and the like.

It is noted that in the present disclosure, the explanation for aryl may apply to arylene and the explanation for heteroaryl may apply to heteroarylene.

Further, substituted may mean that at least one hydrogen atom may be substituted with a substituent.

In one embodiment, R may be selected from the group formed by:

wherein the above radicals are used in combination with the compounds of formula I

The groups are combined.

In one embodiment, the nitrogen-containing compounds of embodiments of the present disclosure are selected from the group consisting of:

the nitrogen-containing compounds are only exemplary nitrogen-containing compounds, and other nitrogen-containing compounds may be included, and are not listed here.

Hereinafter, the synthesis process of the nitrogen-containing compound of the present disclosure will be described in detail by examples. However, the following examples are merely illustrative of the present disclosure and do not limit the present disclosure.

Synthesis of Compound 1:

adding SM1(50g, 362.50mmol), SM2(109.07g, 362.50mmol), tetrakis (triphenylphosphine) palladium (20.95g, 18.16mmol), potassium carbonate (100.20g, 725.00mmol), tetrabutylammonium chloride (5.03g, 18.12mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round-bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give intermediate I-A-1(87.13g, yield 90%).

Adding intermediate I-A-1(87.13g, 326.20mmol), sodium hydroxide (26.09g, 652.42mmol) and NMP (N-methylpyrrolidone) (1054.18g, 10634.36mmol) into a round-bottom flask, heating to reflux, stirring for 3h, cooling the reaction liquid to room temperature, adding dichloromethane (200mL) for extraction, combining organic phases, drying with anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by silica gel column chromatography using methylene chloride as a mobile phase and concentrated to dryness to give intermediate I-A (60.45g, yield 75%).

SM3(5.00g, 21.35mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (50ml), n-butyllithium (1.44g, 22.42mmol) was added dropwise at-78 deg.C, and after addition was complete, trimethyl borate (3.33g, 32.03mmol) was added dropwise after 1h of incubation, and after 1h of incubation was continued, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-B (2.76g, 65% yield) as a white solid.

Adding intermediate I-A (3.0g, 12.14mmol), intermediate I-B (2.41g, 12.14mmol), tetrakis (triphenylphosphine) palladium (0.70g, 0.61mmol), potassium carbonate (3.36g, 24.28mmol), tetrabutylammonium chloride (0.17g, 0.61mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give intermediate I-C-1(3.49g, yield 90%).

Intermediate I-C-1(3.49g, 10.86mmol) was added to a flask containing DCM (dichloromethane) (30ml), NBS (N-succinimide) (5.79g, 32.57mmol) was added, stirred at room temperature overnight, filtered after completion of the reaction to give a crude white product, which was slurried with N-heptane to give intermediate I-C-2(3.5g, 90% yield) as a white solid.

Intermediate I-C-2(3.5g, 10.86mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml), n-butyllithium (0.73g, 11.40mmol) was added dropwise at-78 deg.C, after addition was complete, trimethyl borate (1.69g, 16.29mmol) was added dropwise after 1h of incubation, after 1h of further incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-C (2.97g, 65% yield) as a white solid.

Adding intermediate I-C (2.97g, 8.13mmol), SM4(2.54g, 8.13mmol), tetrakis (triphenylphosphine) palladium (0.47g, 0.41mmol), potassium carbonate (2.25g, 16.26mmol), tetrabutylammonium chloride (0.11g, 0.41mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) to a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; obtained byThe crude product was purified by column chromatography on silica gel using n-heptane as a mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give compound 1(3.95g, yield 88%). The mass spectrum is as follows: 552.64[ M + H ] M/z]⁺。

Synthesis of Compound 2:

SM5(10.00g, 40.30mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (50ml), n-butyllithium (1.44g, 22.42mmol) was added dropwise at-78 deg.C, and after addition was complete, the mixture was incubated for 1 hour, trimethyl borate (3.33g, 32.03mmol) was added dropwise, and after 1 hour of incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and then filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-D-1(5.0g, 58% yield) as a white solid.

Adding intermediate I-A (3.0g, 12.14mmol), intermediate I-D-1(3.45g, 16.18mmol), tetrakis (triphenylphosphine) palladium (0.70g, 0.61mmol), potassium carbonate (3.36g, 24.28mmol), tetrabutylammonium chloride (0.17g, 0.61mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give intermediate I-D-2(4.66g, yield 86%).

Intermediate I-D-2(4.0g, 11.9mmol) was added to a flask containing DCM (dichloromethane) (40ml), NBS (N-succinimide) (6.36g, 35.7mmol) was added, stirred at room temperature overnight, filtered after completion of the reaction to give a crude white product, and slurried with N-heptane to give intermediate I-D-3 as a white solid (3.5g, 94% yield).

Intermediate I-D-3(4.66g, 13.89mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml), n-butyllithium (0.73g, 11.40mmol) was added dropwise at-78 deg.C, after addition was complete, trimethyl borate (1.69g, 16.29mmol) was added dropwise after 1h of incubation, after 1h of further incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-D (2.63g, 50% yield) as a white solid.

Adding intermediate I-D (2.63g, 6.93mmol), SM4(2.54g, 8.13mmol), tetrakis (triphenylphosphine) palladium (0.47g, 0.41mmol), potassium carbonate (2.25g, 16.26mmol), tetrabutylammonium chloride (0.11g, 0.41mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) to a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give compound 2(3.45g, yield 88%). The mass spectrum is as follows: 566.66[ M + H ] M/z]⁺。

Synthesis of Compound 3:

SM6(10.00g, 40.30mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (50ml), n-butyllithium (1.44g, 22.42mmol) was added dropwise at-78 deg.C, and after addition was complete, the mixture was incubated for 1 hour, trimethyl borate (3.33g, 32.03mmol) was added dropwise, and after 1 hour of incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and then filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-E-1(5.0g, 58% yield) as a white solid.

Adding intermediate I-A (3.0g, 12.14mmol), intermediate I-E-1(3.45g, 16.18mmol), tetrakis (triphenylphosphine) palladium (0.70g, 0.61mmol), potassium carbonate (3.36g, 24.28mmol), tetrabutylammonium chloride (0.17g, 0.61mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give intermediate I-E-2(4.66g, yield 86%).

Intermediate I-E-2(4.0g, 11.9mmol) was added to a flask containing DCM (dichloromethane) (40ml), NBS (N-succinimide) (6.36g, 35.7mmol) was added, stirred at room temperature overnight, filtered after completion of the reaction to give a crude white product, and slurried with N-heptane to give intermediate I-E-3(3.5g, 94% yield) as a white solid.

Intermediate I-E-3(4.66g, 13.89mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml), n-butyllithium (0.73g, 11.40mmol) was added dropwise at-78 deg.C, after addition was complete, trimethyl borate (1.69g, 16.29mmol) was added dropwise after 1h of incubation, after 1h of further incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-E (2.63g, 50% yield) as a white solid.

Intermediate I-E-2(4.66g, 13.89mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml), n-butyllithium (0.73g, 11.40mmol) was added dropwise at-78 deg.C, after addition was complete, trimethyl borate (1.69g, 16.29mmol) was added dropwise after 1h of incubation, after 1h of further incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-E (2.63g, 50% yield) as a white solid.

Adding intermediate I-E (2.63g, 6.93mmol), SM4(2.54g, 8.13mmol), tetrakis (triphenylphosphine) palladium (0.47g, 0.41mmol), potassium carbonate (2.25g, 16.26mmol), tetrabutylammonium chloride (0.11g, 0.41mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) to a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give compound 3(3.45g, yield 88%). The mass spectrum is as follows: 566.66[ M + H ] M/z]⁺。

Synthesis of Compound 4:

SM7(5.00g, 21.35mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (50ml), n-butyllithium (1.44g, 22.42mmol) was added dropwise at-78 deg.C, and after addition was complete, trimethyl borate (3.33g, 32.03mmol) was added dropwise after 1h of incubation, and after 1h of incubation was continued, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-F-1(2.76g, 65% yield) as a white solid.

Adding intermediate I-A (3.0g, 12.14mmol), intermediate I-F-1(2.41g, 12.14mmol), tetrakis (triphenylphosphine) palladium (0.70g, 0.61mmol), potassium carbonate (3.36g, 24.28mmol), tetrabutylammonium chloride (0.17g, 0.61mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give intermediate I-F-2(3.49g, yield 90%).

Intermediate I-F-2(3.3g, 10.26mmol) was added to a flask containing DCM (dichloromethane) (30ml), NBS (N-succinimide) (5.48g, 30.80mmol) was added, stirred at room temperature overnight, filtered after completion of the reaction to give a crude white product, and slurried with N-heptane to give intermediate I-F-3(3.5g, 85% yield) as a white solid.

Intermediate I-F-3(3.49g, 10.86mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml), n-butyllithium (0.73g, 11.40mmol) was added dropwise at-78 deg.C, after addition was complete, trimethyl borate (1.69g, 16.29mmol) was added dropwise after 1h of incubation, after 1h of further incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediates I to F (2.97g, 65% yield) as a white solid.

Adding intermediate I-F (2.97g, 8.13mmol), SM4(2.54g, 8.13mmol), tetrakis (triphenylphosphine) palladium (0.47g, 0.41mmol), potassium carbonate (2.25g, 16.26mmol), tetrabutylammonium chloride (0.11g, 0.41mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) to a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give compound 4(3.99g, yield 89%). The mass spectrum is as follows: 552.64[ M + H ] M/z]⁺。

Synthesis of Compound 5:

SM8(10.00g, 32.13mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (50ml), n-butyllithium (1.44g, 22.42mmol) was added dropwise at-78 deg.C, and after addition was complete, trimethyl borate (3.33g, 32.03mmol) was added dropwise after 1h of incubation, and after 1h of incubation was continued, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and then filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-G-1(5.0G, 56% yield) as a white solid.

Adding intermediate I-A (3.0G, 12.14mmol), intermediate I-G-1(4.46G, 16.18mmol), tetrakis (triphenylphosphine) palladium (0.70G, 0.61mmol), potassium carbonate (3.36G, 24.28mmol), tetrabutylammonium chloride (0.17G, 0.61mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give intermediate I-G-2(5.42G, yield 84%).

Intermediate I-G-2(5.42G, 18.30mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml) at-78 deg.C, n-butyllithium (0.73G, 11.40mmol) was added dropwise, after addition was complete, the temperature was held for 1h, trimethyl borate (1.69G, 16.29mmol) was added dropwise, the temperature was further held for 1h, and the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediates I-G (4.04G, 50% yield) as a white solid.

Adding the intermediate I-G (4.04G, 9.13mmol), SM4(2.54G, 8.13mmol), tetrakis (triphenylphosphine) palladium (0.47G, 0.41mmol), potassium carbonate (2.25G, 16.26mmol), tetrabutylammonium chloride (0.11G, 0.41mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round-bottomed flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give compound 5(5.00g, yield 85%). The mass spectrum is as follows: 529.72[ M + H ] M/z]⁺。

Synthesis of Compound 6:

SM9(10.00g, 32.13mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (50ml), n-butyllithium (1.44g, 22.42mmol) was added dropwise at-78 deg.C, and after addition was complete, trimethyl borate (3.33g, 32.03mmol) was added dropwise after 1h of incubation, and after 1h of incubation was continued, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and then filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-H-1(5.0g, 56% yield) as a white solid.

Adding intermediate I-A (3.0g, 12.14mmol), intermediate I-H-1(4.46g, 16.18mmol), tetrakis (triphenylphosphine) palladium (0.70g, 0.61mmol), potassium carbonate (3.36g, 24.28mmol), tetrabutylammonium chloride (0.17g, 0.61mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give intermediate I-H-2(5.42g, yield 84%).

Intermediate I-H-2(5.42g, 18.30mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml) at-78 deg.C, n-butyllithium (0.73g, 11.40mmol) was added dropwise, after addition was complete, the temperature was held for 1H, trimethyl borate (1.69g, 16.29mmol) was added dropwise, the temperature was further held for 1H, and the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-H (4.04g, 50% yield) as a white solid.

Intermediate I-H (4.04g, 9.13mmol), SM4(2.54g, 8.13mmol), tetrakis (triphenylphosphine) palladium (0.47g, 0.41mmol), potassium carbonate (2.2 mmol)5g, 16.26mmol), tetrabutylammonium chloride (0.11g, 0.41mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) were added to a round bottom flask, warmed to 78 ℃ under nitrogen protection, and stirred for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give compound 6(4.94g, yield 84%). The mass spectrum is as follows: 529.72[ M + H ] M/z]⁺。

Synthesis of compound 7:

SM10(10.00g, 63.29mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (50ml), n-butyllithium (1.44g, 22.42mmol) was added dropwise at-78 deg.C, and after addition was complete, trimethyl borate (3.33g, 32.03mmol) was added dropwise after 1h of incubation, and after 1h of incubation was continued, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and then filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-I-1(4.90g, 56% yield) as a white solid.

Adding intermediate I-A (3.0g, 12.14mmol), intermediate I-I-1(1.98g, 16.18mmol), tetrakis (triphenylphosphine) palladium (0.70g, 0.61mmol), potassium carbonate (3.36g, 24.28mmol), tetrabutylammonium chloride (0.17g, 0.61mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give intermediate I-I-2(3.29g, yield 83%).

Intermediate I-I-2(3.29g, 13.14mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml), n-butyllithium (0.73g, 11.40mmol) was added dropwise at-78 deg.C, after addition was complete, trimethyl borate (1.69g, 16.29mmol) was added dropwise after 1h of incubation, after 1h of further incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-I (1.95g, 49% yield) as a white solid.

Adding intermediate I-I (1.95g, 6.74mmol), SM4(2.54g, 8.13mmol), tetrakis (triphenylphosphine) palladium (0.47g, 0.41mmol), potassium carbonate (2.25g, 16.26mmol), tetrabutylammonium chloride (0.11g, 0.41mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round-bottomed flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give compound 7(2.66g, yield 83%). The mass spectrum is as follows: m/z 476.54[ M + H ]]⁺。

Synthesis of compound 8:

SM11(10.00g, 58.12mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (50ml), n-butyllithium (1.44g, 22.42mmol) was added dropwise at-78 deg.C, and after addition was complete, the mixture was incubated for 1 hour, trimethyl borate (3.33g, 32.03mmol) was added dropwise, and after 1 hour of incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and then filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-J-1(4.45g, 56% yield) as a white solid.

Adding intermediate I-A (3.0g, 12.14mmol), intermediate I-J-1(2.21g, 16.18mmol), tetrakis (triphenylphosphine) palladium (0.70g, 0.61mmol), potassium carbonate (3.36g, 24.28mmol), tetrabutylammonium chloride (0.17g, 0.61mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give intermediate I-J-2(3.48g, yield 83%).

Intermediate I-J-2(3.48g, 13.42mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml), n-butyllithium (0.73g, 11.40mmol) was added dropwise at-78 deg.C, after addition was complete, trimethyl borate (1.69g, 16.29mmol) was added dropwise after 1h of incubation, after 1h of further incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediates I-J (2.04g, 50% yield) as a white solid.

Adding intermediate I-J (2.04g, 6.73mmol), SM4(2.54g, 8.13mmol), tetrakis (triphenylphosphine) palladium (0.47g, 0.41mmol), potassium carbonate (2.25g, 16.26mmol), tetrabutylammonium chloride (0.11g, 0.41mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) to a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; the reaction was cooled to room temperature, toluene (200mL) was added for extraction, and the organics were combinedPhase, dried over anhydrous magnesium sulfate, filtered and the solvent removed under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give compound 8(2.81g, yield 86%). The mass spectrum is as follows: 495.57[ M + H ] M/z]⁺。

Synthesis of compound 9:

SM12(10.00g, 58.12mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (50ml), n-butyllithium (1.44g, 22.42mmol) was added dropwise at-78 deg.C, and after addition was complete, the mixture was incubated for 1 hour, trimethyl borate (3.33g, 32.03mmol) was added dropwise, and after 1 hour of incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) is added to adjust the pH to be neutral, then the white crude product is obtained by filtration, and white solid intermediate I-K-1(4.45g, yield is 56%) is obtained by pulping with n-heptane.

Adding intermediate I-A (3.0g, 12.14mmol), intermediate I-K-1(2.21g, 16.18mmol), tetrakis (triphenylphosphine) palladium (0.70g, 0.61mmol), potassium carbonate (3.36g, 24.28mmol), tetrabutylammonium chloride (0.17g, 0.61mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from dichloromethane/ethyl acetate system to give intermediate I-K-2(3.48g, yield 83%).

Intermediate I-K-2(3.48g, 13.42mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml), n-butyllithium (0.73g, 11.40mmol) was added dropwise at-78 deg.C, after addition was complete, trimethyl borate (1.69g, 16.29mmol) was added dropwise after 1h of incubation, after 1h of further incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-K (2.04g, 50% yield) as a white solid.

Adding intermediate I-K (2.04g, 6.73mmol), SM4(2.54g, 8.13mmol), tetrakis (triphenylphosphine) palladium (0.47g, 0.41mmol), potassium carbonate (2.25g, 16.26mmol), tetrabutylammonium chloride (0.11g, 0.41mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give compound 9(2.81g, yield 86%). The mass spectrum is as follows: 495.57[ M + H ] M/z]⁺。

Synthesis of compound 10:

SM13(10.00g, 53.75mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (50ml), n-butyllithium (1.44g, 22.42mmol) was added dropwise at-78 deg.C, and after addition was complete, the mixture was incubated for 1 hour, trimethyl borate (3.33g, 32.03mmol) was added dropwise, and after 1 hour of incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-L-1(4.29g, 53% yield) as a white solid.

Adding intermediate I-A (3.0g, 12.14mmol), intermediate I-L-1(2.44g, 16.18mmol), tetrakis (triphenylphosphine) palladium (0.70g, 0.61mmol), potassium carbonate (3.36g, 24.28mmol), tetrabutylammonium chloride (0.17g, 0.61mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round-bottomed flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give intermediate I-L-2(3.67g, yield 83%).

Intermediate I-L-2(3.67g, 13.42mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml), n-butyllithium (0.73g, 11.40mmol) was added dropwise at-78 deg.C, after addition was complete, trimethyl borate (1.69g, 16.29mmol) was added dropwise after 1h of incubation, after 1h of further incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-L (2.08g, 49% yield) as a white solid.

Adding intermediate I-L (2.08g, 6.55mmol), SM4(2.54g, 8.13mmol), tetrakis (triphenylphosphine) palladium (0.47g, 0.41mmol), potassium carbonate (2.25g, 16.26mmol), tetrabutylammonium chloride (0.11g, 0.41mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round-bottomed flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give compound 10(2.78g, yield 84%).The mass spectrum is as follows: 504.59[ M + H ] M/z]⁺。

Synthesis of compound 11:

SM14(10.00g, 53.75mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (50ml), n-butyllithium (1.44g, 22.42mmol) was added dropwise at-78 deg.C, and after addition was complete, the mixture was incubated for 1 hour, trimethyl borate (3.33g, 32.03mmol) was added dropwise, and after 1 hour of incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-M-1(4.29g, 53% yield) as a white solid.

Adding intermediate I-A (3.0g, 12.14mmol), intermediate I-M-1(2.44g, 16.18mmol), tetrakis (triphenylphosphine) palladium (0.70g, 0.61mmol), potassium carbonate (3.36g, 24.28mmol), tetrabutylammonium chloride (0.17g, 0.61mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give intermediate I-M-2(3.67g, yield 83%).

Intermediate I-M-2(3.67g, 13.42mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml), n-butyllithium (0.73g, 11.40mmol) was added dropwise at-78 deg.C, after addition was complete, trimethyl borate (1.69g, 16.29mmol) was added dropwise after 1h of incubation, after 1h of further incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-M (2.08g, 49% yield) as a white solid.

Adding intermediate I-M (2.08g, 6.55mmol), SM4(2.54g, 8.13mmol), tetrakis (triphenylphosphine) palladium (0.47g, 0.41mmol), potassium carbonate (2.25g, 16.26mmol), tetrabutylammonium chloride (0.11g, 0.41mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) to a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give compound 11(2.78g, yield 84%). The mass spectrum is as follows: 504.59[ M + H ] M/z]⁺。

Synthesis of compound 12:

SM15(10.00g, 48.06mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (50ml), n-butyllithium (1.44g, 22.42mmol) was added dropwise at-78 deg.C, and after addition was complete, trimethyl borate (3.33g, 32.03mmol) was added dropwise after 1h of incubation, and after 1h of incubation was continued, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with N-heptane to give intermediate I-N-1(4.40g, 53% yield) as a white solid.

Adding intermediate I-A (3.0g, 12.14mmol), intermediate I-N-1(2.80g, 16.18mmol), tetrakis (triphenylphosphine) palladium (0.70g, 0.61mmol), potassium carbonate (3.36g, 24.28mmol), tetrabutylammonium chloride (0.17g, 0.61mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using N-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give intermediate I-N-2(4.06g, yield 85%).

Intermediate I-N-2(4.06g, 13.75mmol) was added to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml) and N-butyllithium (0.73g, 11.40mmol) was added dropwise at-78 deg.C, after addition was complete the flask was incubated for 1h and trimethyl borate (1.69g, 16.29mmol) was added dropwise and after further incubation for 1h the flask was warmed to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with N-heptane to give intermediate I-N (2.28g, 49% yield) as a white solid.

Adding intermediate I-N (2.28g, 6.72mmol), SM4(2.54g, 8.13mmol), tetrakis (triphenylphosphine) palladium (0.47g, 0.41mmol), potassium carbonate (2.25g, 16.26mmol), tetrabutylammonium chloride (0.11g, 0.41mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give compound 12(2.97g, yield 84%). The mass spectrum is as follows: 526.60[ M + H ] M/z]⁺。

Synthesis of compound 13:

SM16(10.00g, 47.83mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (50ml), n-butyllithium (1.44g, 22.42mmol) was added dropwise at-78 deg.C, and after addition was complete, trimethyl borate (3.33g, 32.03mmol) was added dropwise after 1h of incubation, and after 1h of incubation was continued, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-O-1(4.41g, 53% yield) as a white solid.

Adding intermediate I-A (3.0g, 12.14mmol), intermediate I-O-1(2.81g, 16.18mmol), tetrakis (triphenylphosphine) palladium (0.70g, 0.61mmol), potassium carbonate (3.36g, 24.28mmol), tetrabutylammonium chloride (0.17g, 0.61mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give intermediate I-O-2(4.02g, yield 84%).

Intermediate I-O-2(4.02g, 13.56mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml) at-78 deg.C, n-butyllithium (0.73g, 11.40mmol) was added dropwise, after addition was complete, the temperature was held for 1h, trimethyl borate (1.69g, 16.29mmol) was added dropwise, the temperature was further held for 1h, and the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and then filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-O (2.31g, 50% yield) as a white solid.

Adding intermediate I-O (2.31g, 6.79mmol), SM4(2.54g, 8.13mmol), tetrakis (triphenylphosphine) palladium (0.47g, 0.41mmol), potassium carbonate (2.25g, 16.26mmol), tetrabutylammonium chloride (0.11g, 0.41mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give compound 13(3.01g, yield 84%). The mass spectrum is as follows: 527.59[ M + H ] M/z]⁺。

Synthesis of compound 14:

SM17(10.00g, 44.03mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (50ml), n-butyllithium (1.44g, 22.42mmol) was added dropwise at-78 deg.C, and after addition was complete, trimethyl borate (3.33g, 32.03mmol) was added dropwise after 1h of incubation, and after 1h of incubation was continued, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-P-1(4.45g, 53% yield) as a white solid.

Adding intermediate I-A (3.0g, 12.14mmol), intermediate I-P-1(3.11g, 16.18mmol), tetrakis (triphenylphosphine) palladium (0.70g, 0.61mmol), potassium carbonate (3.36g, 24.28mmol), tetrabutylammonium chloride (0.17g, 0.61mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give intermediate I-P-2(4.22g, yield 83%).

Intermediate I-P-2(4.22g, 13.42mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml), n-butyllithium (0.73g, 11.40mmol) was added dropwise at-78 deg.C, after addition was complete, trimethyl borate (1.69g, 16.29mmol) was added dropwise after 1h of incubation, after 1h of further incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-P (2.4g, 50% yield) as a white solid.

Adding intermediate I-P (2.40g, 6.70mmol), SM4(2.54g, 8.13mmol), tetrakis (triphenylphosphine) palladium (0.47g, 0.41mmol), potassium carbonate (2.25g, 16.26mmol), tetrabutylammonium chloride (0.11g, 0.41mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give compound 14(3.01g, yield 84%). The mass spectrum is as follows: 545.65[ M + H ] M/z]⁺。

Synthesis of compound 15:

SM18(10.00g, 51.00mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (50ml), n-butyllithium (1.44g, 22.42mmol) was added dropwise at-78 deg.C, and after addition was complete, trimethyl borate (3.33g, 32.03mmol) was added dropwise after 1h of incubation, and after 1h of incubation was continued, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-Q-1(3.92g, 51% yield) as a white solid.

Adding intermediate I-A (3.0g, 12.14mmol), intermediate I-Q-1(2.44g, 16.18mmol), tetrakis (triphenylphosphine) palladium (0.70g, 0.61mmol), potassium carbonate (3.36g, 24.28mmol), tetrabutylammonium chloride (0.17g, 0.61mmol), toluene (30mL), ethanol (16mL) and deionized water (8mL) into a round bottom flask, heating to 78 ℃ under nitrogen protection, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give intermediate I-Q-2(3.75g, yield 85%).

Intermediate I-Q-2(3.75g, 13.72mmol) was added dropwise to a 250ml three-necked flask containing THF (tetrahydrofuran) (30ml), n-butyllithium (0.73g, 11.40mmol) was added dropwise at-78 deg.C, after addition was complete, trimethyl borate (1.69g, 16.29mmol) was added dropwise after 1h of incubation, after 1h of further incubation, the mixture was allowed to warm to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and the mixture was filtered to give a crude white product, which was slurried with n-heptane to give intermediate I-Q (2.18g, 50% yield) as a white solid.

Intermediate I-Q (2.18g, 6.87mmol), SM4(2.54g, 8.13mmol), tetrakis (triphenylphosphine) palladium (0.47g, 0.41mmol), potassium carbonate (2.25g, 16.26mmol), tetrabutylammonium chloride (0.11g, 0.41mmol), toluene (30mL), ethanol (16mL) andadding deionized water (8mL) into a round-bottom flask, heating to 78 ℃ under the protection of nitrogen, and stirring for 10 hours; cooling the reaction solution to room temperature, adding toluene (200mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using n-heptane as the mobile phase, followed by recrystallization from a dichloromethane/ethyl acetate system to give compound 15(2.87g, yield 83%). The mass spectrum is as follows: 504.59[ M + H ] M/z]⁺。

The present disclosure also provides an electronic component, as shown in fig. 1, including an anode 1 and a cathode 5 disposed opposite to each other, and a functional layer 3 disposed between the anode 1 and the cathode 5, wherein the functional layer 3 includes the nitrogen-containing compound according to any one of the above embodiments.

In the electronic element disclosed by the invention, as the functional layer 3 comprises a nitrogen-containing compound which combines a substituent group with nitrogen heterocycle onto a common electron transport group 2, 4-diphenyl-1, 3, 5-triazine through a 2, 4-disubstituted dibenzofuran (or dibenzothiophene) group, on one hand, the molecule has an electron-deficient large conjugated plane structure formed by directly combining the triazine and the 4 th position of dibenzofuran (or dibenzothiophene), which is beneficial to improving the electron transport rate, and further can improve the photoelectric conversion efficiency of the electronic element; on the other hand, nitrogen heterocycles can be introduced into the structure of the dibenzofuran (or dibenzothiophene) with the 2 nd site and the triazine being meta (non-conjugated) or para, so that the electron injection capability of the electronic element can be effectively enhanced, and the photoelectric conversion efficiency and the service life of the device can be further improved.

The anode 1 may be a material that facilitates hole injection into the functional layer 3, for example, the anode 1 material may be a metal, an alloy, a metal oxide, or the like, for example, it may be nickel, platinum, vanadium, chromium, copper, zinc, gold, or an alloy thereof, and may also be zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); of course, the anode 1 material can also be other, for example, a composition such as: ZnO Al SnO₂Sb, conductive polymer (poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene)](PEDT), polypyrrole and polyaniline), of course, of the anode 1The material is not limited thereto, and may be other materials, which are not listed here. Preferably, the anode 1 material may be Indium Tin Oxide (ITO), which may be a thin film coated on the surface of the functional layer 3 far from the anode 1, and the thickness of the thin film may be

For example, it may be

Or

Of course, other thicknesses are possible and are not listed here.

The cathode 5 may be a material that facilitates electron injection into the functional layer 3, for example, the cathode 5 material may be a metal or alloy material, for example, it may be magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead or their alloys, or a multilayer material, such as: LiF/Al, Liq/Al, LiO₂Al, LiF/Ca, LiF/Al and BaF₂The material of the cathode 5 is not limited to this, and may be other materials, which are not listed here. Preferably, the cathode 5 material may be aluminum. The thickness of the cathode 5 may be

Or

Of course, other thicknesses are possible and are not particularly limited herein.

In an embodiment, the functional layer 3 may include an electron transport layer 34, and the electron transport layer 34 may include any one of the nitrogen-containing compounds described above. For example, the electron transport layer 34 can be a thin film that can be used for electron transport and can have a thickness of

For example, it may be

Or

Of course, other thicknesses are possible and are not listed here.

The functional layer 3 may further include a light emitting layer 33, an electron blocking layer 32 and a hole transporting layer 31, wherein the light emitting layer 33 may be disposed on a side of the electron transporting layer 34 away from the cathode 5, and may provide a composite or separate place for electrons and holes, and the electrons and holes may be combined in the light emitting layer 33 to generate excitons, so as to achieve the effect of emitting light. The electron blocking layer 32 may be disposed on a side of the light emitting layer 33 away from the electron transport layer 34, and may be used to block the transport of electrons to the anode 1. The hole transport layer 31 may be disposed on a side of the electron blocking layer 32 away from the light emitting layer 33, and may be used for hole transport. The electronic element may include an anode 1, a hole transport layer 31, a light emitting layer 33, an electron transport layer 34, and a cathode 5, which are stacked.

Meanwhile, the electronic component of the embodiment of the present disclosure may further include a hole injection layer 2 and an electron injection layer 4, wherein: the hole injection layer 2 may be provided between the functional layer 3 and the anode 1; the electron injection layer 4 may be provided between the functional layer 3 and the cathode 5. The electronic component may be, for example, an organic electroluminescent device.

In other embodiments, the electronic component may also be a solar cell, as shown in fig. 2, which may be an organic solar cell, for example. It mainly includes a cathode 400, an anode 200 and a functional layer 300, the functional layer 300 can be disposed between the cathode 400 and the anode 200, and the functional layer 300 can include a nitrogen-containing compound in any embodiment of the disclosure, and can be used to increase the transport rate of excitons. In one embodiment, the functional layer 300 may include an electron transport layer 303, a hole transport layer 301, and a photosensitive active layer 302, the anode 200 may be formed on a substrate 100, the anode 200 may be a thin film attached to the substrate 100, the hole transport layer 301 may be formed on a surface of the anode 200 away from the substrate 100, the photosensitive active layer 302 may be formed on a surface of the hole transport layer 301 away from the anode 200, the electron transport layer 303 may be formed on a surface of the photosensitive active layer 302 away from the hole transport layer 301, the electron transport layer 303 may include a nitrogen-containing compound according to any of the embodiments of the present disclosure, and the cathode 400 may be formed on a surface of the electron transport layer 303 away from the photosensitive active layer 302. When sunlight irradiates the solar cell, electrons in the photosensitive active layer 302 obtain energy to jump to generate excitons, the electrons move to the cathode 400 and the holes move to the anode 200 under the assistance of the electron transport layer 303 and the hole transport layer 301, so that a potential difference can be generated between the cathode 400 and the anode 200 of the solar cell, and a power generation function is further realized. In the process, the compound disclosed by the invention can be used for enhancing the transmission rate of electrons in the electron transmission layer 303, avoiding recombination of electrons and holes, further increasing the quantity of the electrons transmitted to the cathode 400, thereby improving the open-circuit voltage of the solar cell and improving the photoelectric conversion efficiency, and as the nitrogen-containing compound disclosed by the invention can introduce nitrogen heterocycles to the structure that the 2 nd position of dibenzofuran (or dibenzothiophene) and the triazine are meta (nonconjugated) or para positions, the electron injection capability of the material can be effectively enhanced, and the efficiency and the service life of the device can be further improved. Hereinafter, the organic electroluminescent device of the present disclosure will be described in detail by way of examples, taking the organic electroluminescent device as an example. However, the following examples are merely illustrative of the present disclosure and do not limit the present disclosure.

The electronic component can be applied to various electronic devices, as shown in fig. 3, which can be a display device, a lighting device, an optical communication device or other types of electronic devices, for example, which can include but are not limited to a computer, a mobile phone 500, a television, electronic paper, an emergency light, an optical module, and the like.

Production and evaluation examples of organic electroluminescent device

Example 1: fabrication of organic electroluminescent devices

The anode 1 was prepared by the following procedure: the thickness of ITO is set as

The ITO substrate of (1) was cut into a size of 40mm (length) × 40mm (width) × 0.7mm (thickness), prepared into an experimental substrate having a cathode 5, an anode 1 and an insulating layer pattern using a photolithography process, and UV ozone and O were used₂:N₂The plasma surface treatment is performed to increase the work function of the anode 1, and the ITO substrate surface may be cleaned by using an organic solvent to remove impurities and oil stains on the ITO substrate surface, for example, the ITO substrate may be ultrasonically cleaned by using an organic solvent such as ethanol, acetone, or isopropyl alcohol to remove impurities on the ITO substrate surface. It should be noted that the ITO substrate may be cut into other sizes according to actual needs, and the size of the ITO substrate in the disclosure is not particularly limited.

HAT-CN (structural formula can be seen below) was vacuum-evaporated on an experimental substrate (anode 1) to a thickness of

And NPB (structural formula can be seen hereinafter) is vacuum-evaporated on the hole injection layer 2(HIL) to form a layer having a thickness of

The hole transport layer 31 (HTL).

A compound TCTA (structural formula can be seen below) was vapor-deposited on the hole transport layer 31(HTL) to a thickness of

Electron blocking layer 32 (EBL). Of course, the electron blocking layer 32(EBL) may have other thicknesses, and is not particularly limited.

BD-1 (structure formula shown below) was simultaneously doped with compound α -ADN (structure formula shown below) by evaporation on the electron blocking layer 32(EBL) at a film thickness ratio of 20:1

The light emitting layer 33 (EML). In one embodiment of the present disclosure, the film thickness ratio may be controlled by the evaporation rate. Examples of such applications areIn other words, the compound α -ADN and the compound BD-1 can be simultaneously evaporated to form the light-emitting layer, wherein the evaporation rate of the compound α -ADN is 20 times the deposition rate of the compound BD-1.

The compound 1 and LiQ (structural formula can be seen hereinafter) were vapor-deposited as an electron transport layer 34(ETL) on the light-emitting layer 33(EML) at a film thickness ratio of 2:1, and the thickness of the electron transport layer 34 may be such that

Of course, the electron transport layer 34(ETL) may have other thicknesses, and is not limited herein.

Silver (Ag) and magnesium (Mg) were vapor-deposited on the electron transport layer 34(ETL) at a film thickness ratio of 10:1 to form a film having a thickness of

And a cathode 5.

Further, the cathode 5 is vapor-deposited to a thickness of

The compound CP-1 (structural formula can be seen below) as a capping layer (CPL), thereby completing the fabrication of an organic light-emitting device.

Examples 2 to 15

An organic electroluminescent device was fabricated in the same manner as in example 1, except that compounds 2 to 15 were used instead of compound 1 in forming the Electron Transport Layer (ETL). The performance parameters of each device fabricated are detailed in table 1.

Comparative examples 1 to 4

In comparative examples 1 to 4, organic electroluminescent devices were fabricated in the same manner as in example 1, except that compounds a to D were used as the Electron Transport Layer (ETL) instead of compound 1, respectively. Wherein the structural formulas of the compounds A to D are respectively shown as follows:

namely: comparative example 1 an organic electroluminescent device was manufactured using compound a; comparative example 2 an organic electroluminescent device was produced using compound B; comparative example 3 an organic electroluminescent device was produced using compound C; comparative example 4 an organic electroluminescent device was produced using compound D; the properties of each device prepared are detailed in table 1. Wherein IVL (Current, Voltage, Brightness) data are compared at 10mA/cm²As a result of the test under, T95 life was 15mA/cm²Test results at current density.

TABLE 1 device Performance of examples 1-15 and comparative examples 1-4

As can be seen from table 1, the compounds 1 to 15 used as the Electron Transport Layer (ETL) have the operating voltage of 0.36V at the maximum, the luminous efficiency (Cd/a) improved by at least 19.6%, the external quantum efficiency improved by at least 18.9%, and the lifetime improved by at least 34.8% as compared with the comparative examples 1,2, 3, and 4 using the known compounds a, B, C, and D.

According to the preparation method, triazine is used for replacing dibenzofuran (or dibenzothiophene) as a core structure, and another type of heterocyclic group is introduced, so that compared with comparative examples 3 and 4, the molecular symmetry is reduced, the crystallinity of the material is reduced, the electron injection capability is enhanced, and the efficiency and the service life of the device are improved.

The present disclosure also provides an electronic device, which may include the electronic component according to any of the above embodiments, and the beneficial effects and specific details of the electronic device may refer to the electronic component, which are not described herein again. For example, the electronic device may be a display device, a lighting device, an optical communication device or other types of electronic devices, such as but not limited to a computer, a mobile phone 500, a television, electronic paper, an emergency light, an optical module, and of course, other devices or apparatuses may also be used, and are not limited herein.

Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. This application is intended to cover any variations, uses, or adaptations of the disclosure following, in general, the principles of the disclosure and including such departures from the present disclosure as come within known or customary practice within the art to which the disclosure pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.

Claims

1. The nitrogen-containing compound is characterized in that the structural general formula of the nitrogen-containing compound is shown as formula I:

wherein X is oxygen or sulfur;

2. The nitrogen-containing compound of claim 1, wherein R is selected from the group consisting of: a substituted or unsubstituted heterocycloalkyl group having 3 to 5 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 15 ring-forming carbon atoms.

3. The nitrogen-containing compound of claim 1, wherein L is selected from the group consisting of: a single bond, a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, or a substituted or unsubstituted heteroarylene group having 5 to 12 carbon atoms.

4. The nitrogen-containing compound of claim 1 or 3, wherein L is selected from the group consisting of: a single bond, phenylene, dimethylfluorenylene, biphenylene, naphthylene, or terphenylene.

5. The nitrogen-containing compound of claim 1, wherein L is selected from the group consisting of:

Group bonding;

represents the above groups for binding to the R group in formula I.

6. The nitrogen-containing compound of claim 1, wherein R is selected from the group consisting of:

The groups are combined.

7. The nitrogen-containing compound of claim 1, wherein the nitrogen-containing compound is selected from the group consisting of:

8. an electronic component comprising an anode and a cathode disposed opposite to each other, and a functional layer disposed between the anode and the cathode;

the functional layer contains the nitrogen-containing compound according to any one of claims 1 to 7.

9. The electronic component according to claim 8, wherein the functional layer comprises an electron transporting layer comprising the nitrogen-containing compound according to any one of claims 1 to 7.

10. The electronic component according to claim 8, wherein the electronic component is an organic electroluminescent device or a solar cell.

11. An electronic device, characterized in that it comprises an electronic component according to any one of claims 8-10.