CN111018843B - Compound, electronic element and electronic device - Google Patents

Compound, electronic element and electronic device Download PDF

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CN111018843B
CN111018843B CN201911057785.5A CN201911057785A CN111018843B CN 111018843 B CN111018843 B CN 111018843B CN 201911057785 A CN201911057785 A CN 201911057785A CN 111018843 B CN111018843 B CN 111018843B
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CN111018843A (en
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杨敏
李昕轩
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Shaanxi Lighte Optoelectronics Material Co Ltd
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    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D—HETEROCYCLIC COMPOUNDS
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    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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Abstract

The application provides a compound, an electronic element and an electronic device, and relates to the technical field of organic materials. The compound is shown as formula I, wherein, X1、X2And X3Are the same or different and are each independently selected from: carbon or nitrogen, wherein X1、X2And X3Carbon is not used at the same time; l is selected from: single bond, arylene, heteroarylene, aralkylene, heteroaralkylene; ar (Ar)1Selected from: alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, alkylamino, arylamino, aralkylamino; ar (Ar)2、Ar3Are the same or different and are each independently selected from: cycloalkyl, aryl, heteroaryl, alkoxy, alkylamino, arylamino, aralkylamino. The compound can reduce the working voltage of an electronic element, improve the luminous efficiency of the electronic element and prolong the service life of a device.
Figure DDA0002256984480000011

Description

Compound, electronic element and electronic device
Technical Field
The application relates to the technical field of organic materials, in particular to a compound, an electronic element and an electronic device.
Background
In recent years, with the development of semiconductor technology, electronic components have been widely used, for example: an Organic electroluminescent device (OLED) is widely applied to a display device because of its advantages of simple structure, high brightness, high efficiency, active light emission, fast response speed, high resolution, and the like, and its working principle is as follows: under the action of an electric field, an organic compound is excited by a current and the electric field to emit light. Therefore, the electrical characteristics of the organic compound play a crucial role in device performance.
The existing organic compounds used for electronic elements mainly comprise oxazoles, imidazoles, oxadiazoles, triazoles, benzodiazoles, pyridines, pyrimidines, pyrazines, quinolines, phenanthrolines and quinoxalines, but the Lowest Unoccupied Molecular Orbital (LUMO) of the compounds is higher, the electron transport capability is poorer, so that the problems of working voltage rise, luminous efficiency reduction, service life shortening and the like can occur when an organic electroluminescent device is driven.
This has also been investigated in the prior art literature, for example: patent document CN109575001A and patent document US2019198780a 1.
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 application and therefore may include information that does not constitute prior art known to a person of ordinary skill in the art.
Disclosure of Invention
It is an object of the present invention to overcome the above-mentioned deficiencies in the prior art and to provide a 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 application, there is provided a compound having a general structural formula as shown in formula I:
Figure BDA0002256984460000011
wherein, X1、X2And X3Are the same or different and are each independently selected from: carbon or nitrogen, wherein X1、X2And X3Carbon is not used at the same time;
l is selected from: a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 1 to 30 carbon atoms, a substituted or unsubstituted aralkylene group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroaralkylene group having 2 to 30 carbon atoms;
Ar1selected from: substituted or unsubstituted carbonAn alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms;
Ar2、Ar3are the same or different and are each independently selected from: a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms.
According to one aspect of the present application, 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 application, there is provided an electronic device including the electronic component of any one of the above.
The application provides a compound, electronic component and electronic device, with nitrogenous hexahydric heteroaryl and dibenzofuran and arylamine combine, especially with the triazine group and the pyrimidine group in the nitrogenous hexahydric heteroaryl and dibenzofuran and arylamine combine, on the one hand, because nitrogenous hexahydric heteroaryl has the LUMO energy level that is lower than current compound, can reduce the energy level and pour into the barrier, and then reduce driving voltage. Meanwhile, the nitrogen-containing hexabasic heteroaryl has a stable structure, is not easy to decompose, and has strong high-temperature resistance, so that the service life is prolonged. On the other hand, the nitrogen-containing six-membered heteroaryl has higher electron affinity, is easy to accept electrons and has higher electron mobility. In addition, the benzofuran derivative containing the furan structure has good thermal stability, the aryl amine derivative has lower ionization energy, and the N atom has strong electron donating capability and shows higher hole mobility, so that electrons and holes rapidly move to a recombination region to realize composite luminescence, dynamic balance is achieved, and the efficiency of the device is 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 application.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and together with the description, serve to explain the principles of the application. It is obvious that the drawings in the following description are only some embodiments of the application, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is a schematic structural view of an organic electroluminescent device according to an embodiment of the present application.
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 present application.
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. a hole blocking layer; 35. 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 application.
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.
In the context of the present application, it is,
Figure BDA0002256984460000033
refers to a bond to another substituent.
In the present application, aryl refers to an optional functional group or substituent derived from an aromatic hydrocarbon ring, including monocyclic aryl and polycyclic aryl. The number of carbon atoms in the aryl group is 6 to 30, and it may be 6, 10, 12, 14, 15, 16, 18, 20, 21, 24, 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, and the like.
In the present application, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.
When the fluorenyl group is substituted, include
Figure BDA0002256984460000031
And the like. However, the compound is not limited thereto.
In this application, 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 and Si. The number of carbon atoms in the heteroaryl group is 3 to 20, and it may be 3,5, 11, 12, 13, 14, 15, 18, 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.
In the present application, arylene refers to a 2-valent organic group from which any of the hydrogen radicals in the above-mentioned aryl groups is removed.
In the present disclosure, heteroarylene refers to a heteroaryl group having two bonding sites, i.e., a divalent group. The description of heteroaryl provided above may apply to heteroarylenes, except that the heteroarylenes are each divalent groups.
The embodiment of the application provides a compound, and the structural general formula of the compound is shown as the formula I:
Figure BDA0002256984460000032
wherein, X1、X2And X3Are the same or different and are each independently selected from: carbon or nitrogen, wherein X1、X2And X3Carbon is not used at the same time;
l is selected from: a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 1 to 30 carbon atoms, a substituted or unsubstituted aralkylene group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroaralkylene group having 2 to 30 carbon atoms;
Ar1selected from: a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms;
Ar2、Ar3are the same or different and are each independently selected from: a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atomsOr an unsubstituted arylamino group having 6 to 30 carbon atoms or a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms.
The compound provided by the application can reduce the driving voltage because the nitrogen-containing hexabasic heteroaryl is combined with dibenzofuran and aryl amine, especially the triazine group and pyrimidine group in the nitrogen-containing hexabasic heteroaryl are combined with dibenzofuran and aryl amine, and on one hand, the energy level injection barrier is reduced because the nitrogen-containing hexabasic heteroaryl has a lower LUMO energy level than the existing compound. Meanwhile, the nitrogen-containing hexabasic heteroaryl has a stable structure, is not easy to decompose, and has strong high-temperature resistance, so that the service life is prolonged. On the other hand, the nitrogen-containing six-membered heteroaryl has higher electron affinity, is easy to accept electrons and has higher electron mobility. Meanwhile, the benzofuran derivative containing the furan structure has good thermal stability, the aryl amine derivative has lower ionization energy, and the N atom in the benzofuran derivative has strong electron donating capability and shows higher hole mobility, so that electrons and holes rapidly move to a recombination region, recombination luminescence is realized, dynamic balance is achieved, and the efficiency of the device is further improved.
The following details each of the parts of the compounds of the embodiments of the present application:
the structural general formula of the compound is shown as formula I:
Figure BDA0002256984460000041
wherein, X1、X2And X3May be the same or different and are each independently selected from: carbon or nitrogen, wherein X1、X2And X3Not carbon at the same time.
L is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 1 to 30 carbon atoms, a substituted or unsubstituted aralkylene group having 7 to 30 carbon atoms, and a substituted or unsubstituted heteroaralkylene group having 2 to 30 carbon atoms. In one embodiment, L is selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, and a substituted or unsubstituted heteroarylene group having 6 to 20 carbon atoms. For example, the number of carbon atoms is 6, 10, 14, 18 or 20, although other numbers are possible and are not listed here.
Ar1Selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, of course, Ar1Are selected from other groups, for example, substituted or unsubstituted heteroaromatic amino groups having 3 to 30 carbon atoms, which are not listed here.
In one embodiment, Ar1Is selected from aryl groups having 6 to 18 carbon atoms, for example 6, 10, 12, 14, 15 or 18 carbon atoms, although the number of carbon atoms may be other, and is not listed here. Ar (Ar)1And from heteroaryl having 3 to 12 carbon atoms, for example 3,4, 5, 7, 9, 11 or 12 carbon atoms, although other numbers of carbon atoms are possible and not listed here.
In one embodiment, Ar1Selected from the group formed by:
Figure BDA0002256984460000051
wherein the above radicals are used in combination with the compounds of formula I
Figure BDA0002256984460000052
The groups are combined.
Ar2And Ar3May be the same or different and each is independently selected from substituted or unsubstituted rings having 3 to 12 carbon atomsAn alkyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms.
In one embodiment, Ar2And Ar3Selected from: an aryl group having 6 to 25 carbon atoms or a heteroaryl group having 3 to 12 carbon atoms. For example, Ar2And Ar3Selected from aryl groups having 6 to 25 carbon atoms, for example: the number of carbon atoms is 6, 10, 12, 15, 18 or 25, although other numbers are possible and are not listed here. Ar (Ar)2And Ar3Selected from heteroaryl groups having 3 to 12 carbon atoms, such as: the number of carbon atoms is 3,5, 7, 9, 11 or 12, although other numbers are possible and are not listed here.
In one embodiment, Ar2And Ar3May be the same or different, and Ar2And Ar3Each independently selected from the group consisting of:
Figure BDA0002256984460000061
wherein the above radicals are used in combination with the compounds of formula I
Figure BDA0002256984460000062
The groups are combined.
In one embodiment, L, Ar1、Ar2And Ar3The substituents may be the same or different and are each independently selected from: hydrogen, deuterium, cyano, nitro, halogen, hydroxy, alkyl, cycloalkyl, aralkyl, aryl, heteroaryl, heteroaralkyl, alkoxy, alkylamino, arylamino, aralkylamino, heteroaralkylamino.
For example, Ar1、Ar2And Ar3May be the same or differentAre different from, and each independently selected from: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, spirofluorenyl, pyridyl, quinolyl, pyrimidinyl, carbazolyl, dibenzofuranyl, dibenzothienylisoquinoline, benzothienyl, benzofuranyl, benzopyridyl, adamantyl, perylenyl, thiopyranyl, pyrazinyl, phenazinyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, indolyl, carbazolyl, indolocarbazolyl, acridinyl, quinazolinyl, quinoxalinyl, phenanthrolinyl. Of course, Ar1、Ar2And Ar3And are each independently selected from other groups, and are not particularly limited herein.
In one embodiment, the compounds of the present application are selected from the group consisting of:
Figure BDA0002256984460000071
Figure BDA0002256984460000081
Figure BDA0002256984460000091
Figure BDA0002256984460000101
Figure BDA0002256984460000111
Figure BDA0002256984460000121
Figure BDA0002256984460000131
Figure BDA0002256984460000141
Figure BDA0002256984460000151
Figure BDA0002256984460000161
Figure BDA0002256984460000171
Figure BDA0002256984460000181
it should be noted that the above compounds are only exemplary compounds, and other compounds may be included, which are not listed here.
Hereinafter, the synthesis process of the compound of the present application will be described in detail by examples. However, the following examples are merely illustrative of the present application and do not limit the present application.
Preparation of intermediate I-1:
2,4, 6-trichloro-1, 3, 5-triazine (100g, 542.27mmol) and 800ml of anhydrous tetrahydrofuran were put into a 3L reaction flask, and stirred at 0 ℃ under nitrogen. 97.93ml (1mol/L) of phenylmagnesium bromide (obtained by reacting bromobenzene with metallic magnesium) was added dropwise thereto and allowed to warm to room temperature naturally, followed by stirring for 1 hour. 2mol/L hydrochloric acid aqueous solution was added to the reaction solution, followed by washing with methylene chloride and ultrapure water. After drying over anhydrous magnesium sulfate and filtration through silica gel, the filtrate was concentrated under reduced pressure and recrystallized from dichloromethane and n-heptane to give intermediate I-1(98g, yield 80%).
Preparation of intermediate I-2:
A3L reaction flask was charged with 98g (433.44 mmol) of intermediate I-1, SM1(127.51g, 433.44mmol), 1000ml of anhydrous tetrahydrofuran, palladium acetate (2.92g, 13.0mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (12.39g, 26.00mmol), and potassium acetate (127.61g, 1300.31mmol), and stirred under reflux under nitrogen for 2 hours. The reaction solution was cooled to room temperature, extracted with methylene chloride and ultrapure water, and washed. Dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure, followed by column purification using dichloromethane and n-heptane to give intermediate I-2(124.06g, yield 80%).
Preparation of intermediate I-3:
A1L reaction flask was charged with (76.68g, 214.30mmol) of intermediate I-2, m-bromobenzeneboronic acid (43.03g, 214.31mmol) and 620ml of 1, 4-dioxane, and stirred at 60 ℃ under a nitrogen atmosphere, followed by addition of tetrakis (triphenyl) phosphine palladium (12.38g, 10.72mmol) and 50ml of an aqueous solution of potassium carbonate (59.24g, 428.62mmol), and stirring at elevated temperature under reflux overnight. The reaction solution was cooled to room temperature, and the solid was washed with methanol and ultrapure water and recrystallized from toluene to obtain intermediate I-3(82g, yield 80%).
Preparation of intermediate I-4:
A1L reaction flask was charged with (82.0g, 171.44mmol) of intermediate I-3, p-bromophenylboronic acid (34.42g, 171.44mmol), and 620ml of 1, 4-dioxane, and stirred at 60 ℃ under a nitrogen atmosphere, followed by addition of tetrakis (triphenyl) phosphine palladium (12.38g, 10.72mmol) and 50ml of an aqueous solution of potassium carbonate (59.24g, 428.62mmol), and stirring at elevated temperature under reflux overnight. The reaction solution was cooled to room temperature, and the solid was washed with methanol and ultrapure water and recrystallized from toluene to obtain intermediate I-4(75.08g, yield 79%).
In one embodiment, compound X is obtained by reacting intermediate I-4 with compound SM-A, wherein X can be 1,2, 3,4, 5, 6, 7, 8 or 9, the synthesis process is shown in the reaction formula 1, the compound SM-A can be at least one of diphenylamine, N- (4-biphenyl) -2-naphthylamine, N-phenyl-4-benzidine, N-phenyl-2 (9, 9-dimethyl-9H-fluorene) amine, di (4-biphenyl) amine, 1-naphthylaminobenzene, N-phenyl-2-naphthylamine or N-phenyl- [1,1',4', 1' -terphenyl ] -4-amine, and each type of compound SM-A has a compound X corresponding thereto. For example, the reaction formula 1 is:
Figure BDA0002256984460000191
synthesis of Compound 1:
Figure BDA0002256984460000201
a100 mL reaction flask was charged with intermediate I-4(5.00g, 9.02mmol), diphenylamine (1.53g, 9.02mmol), tris (dibenzylideneacetone) dipalladium (0.08g, 0.09mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl (0.07g, 0.18mmol), sodium tert-butoxide (1.30g, 13.53mmol) and toluene solvent (50mL), warmed to 110 ℃ under nitrogen, heated under reflux and stirred for 3 h. After the reaction solution was cooled to room temperature, the reaction solution was extracted with dichloromethane and water, the organic layer was dried over anhydrous magnesium sulfate and filtered, and after filtration, the filtrate was passed through a short silica gel column, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization using a dichloromethane/n-heptane system to obtain compound 1(4.40g, yield: 79%). The mass spectrum is as follows: m/z 642.8(M + H)+。
Synthesis of Compound 2:
a100 mL reaction flask was charged with intermediate I-4(5.00g, 9.02mmol), N- (4-biphenyl) -2-naphthylamine (2.66g, 9.01mmol), tris (dibenzylideneacetone) dipalladium (0.08g, 0.09mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl (0.07g, 0.18mmol), sodium tert-butoxide (1.30g, 13.53mmol) and toluene solvent (50mL), heated to 110 ℃ under nitrogen, and stirred under reflux for 3 h. After the reaction solution was cooled to room temperature, the reaction solution was extracted with dichloromethane and water, the organic layer was dried over anhydrous magnesium sulfate and filtered, and after filtration, the filtrate was passed through a short silica gel column, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization using a dichloromethane/n-heptane system to obtain compound 2(4.85g, yield: 70%). The mass spectrum is as follows: 768.9(M + H) M/z+。
The structure of the compound 2 obtained is shown below:
Figure BDA0002256984460000202
synthesis of Compound 3:
a100 mL reaction flask was charged with intermediate I-4(5.00g, 9.02mmol), N-phenyl-4-benzidine (2.21g, 9.02mmol), tris (dibenzylideneacetone) dipalladium (0.08g, 0.09mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl (0.07g, 0.18mmol), sodium tert-butoxide (1.30g, 13.53mmol) and toluene solvent (50mL), heated to 110 ℃ under nitrogen, and stirred under reflux for 3 h. After the reaction solution was cooled to room temperature, the reaction solution was extracted with dichloromethane and water, the organic layer was dried over anhydrous magnesium sulfate and filtered, and after filtration, the filtrate was passed through a short silica gel column, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization using a dichloromethane/n-heptane system to obtain compound 3(4.73g, yield: 73%). The mass spectrum is as follows: m/z 718.9(M + H)+。
The structure of the compound 3 obtained is shown below:
Figure BDA0002256984460000211
synthesis of Compound 4:
a100 mL reaction flask was charged with intermediate I-4(5.00g, 9.02mmol), N-phenyl-2 (9, 9-dimethyl-9H-fluorene) amine (2.57g, 9.02mmol), tris (dibenzylideneacetone) dipalladium (0.08g, 0.09mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl (0.07g, 0.18mmol), sodium tert-butoxide (1.30g, 13.53mmol) and toluene solvent (50mL), heated to 110 ℃ under nitrogen, heated to reflux and stirred for 3H. After the reaction solution was cooled to room temperature, the reaction solution was extracted with dichloromethane and water, the organic layer was dried over anhydrous magnesium sulfate and filtered, and after filtration, the filtrate was passed through a short silica gel column, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization using a dichloromethane/n-heptane system to obtain compound 4(4.85g, yield: 71%). The mass spectrum is as follows: 758.9 (M/z)+H)+。
The structure of the compound 4 obtained is shown below:
Figure BDA0002256984460000221
synthesis of Compound 5:
a100 mL reaction flask was charged with intermediate I-4(5.00g, 9.02mmol), bis (4-biphenylyl) amine (2.89g, 9.02mmol), tris (dibenzylideneacetone) dipalladium (0.08g, 0.09mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl (0.07g, 0.18mmol), sodium tert-butoxide (1.30g, 13.53mmol) and toluene solvent (50mL), heated to 110 ℃ under nitrogen, and stirred under reflux for 3 h. After the reaction solution was cooled to room temperature, the reaction solution was extracted with dichloromethane and water, the organic layer was dried over anhydrous magnesium sulfate and filtered, after which the filtrate was passed through a short silica gel column, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization using a dichloromethane/n-heptane system to obtain compound 5(5.15g, yield: 72%). The mass spectrum is as follows: m/z 795.0(M + H)+。
The structure of the compound 5 obtained is shown below:
Figure BDA0002256984460000222
synthesis of Compound 6:
a100 mL reaction flask was charged with intermediate I-4(5.00g, 9.02mmol), 1-naphthylaminobenzene (1.98g, 9.02mmol), tris (dibenzylideneacetone) dipalladium (0.08g, 0.09mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl (0.07g, 0.18mmol), sodium tert-butoxide (1.30g, 13.53mmol) and toluene solvent (50mL), heated to 110 ℃ under nitrogen, and stirred under reflux for 3 h. After the reaction solution was cooled to room temperature, the reaction solution was extracted with dichloromethane and water, the organic layer was dried over anhydrous magnesium sulfate and filtered, and after filtration, the filtrate was passed through a short silica gel column, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization using a dichloromethane/n-heptane system to obtain compound 5(4.55g, yield: 73%). The mass spectrum is as follows: m/z 692.8(M + H)+。
The structure of the compound 6 obtained is shown below:
Figure BDA0002256984460000231
synthesis of compound 7:
a100 mL reaction flask was charged with intermediate I-4(5.00g, 9.02mmol), N-phenyl-2-naphthylamine (1.98g, 9.02mmol), tris (dibenzylideneacetone) dipalladium (0.08g, 0.09mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl (0.07g, 0.18mmol), sodium tert-butoxide (1.30g, 13.53mmol) and toluene solvent (50mL), heated to 110 ℃ under nitrogen, and stirred under reflux for 3 h. After the reaction solution was cooled to room temperature, the reaction solution was extracted with dichloromethane and water, the organic layer was dried over anhydrous magnesium sulfate and filtered, and after filtration, the filtrate was passed through a short silica gel column, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization using a dichloromethane/n-heptane system to obtain compound 7(4.36g, yield: 70%). The mass spectrum is as follows: m/z 692.8(M + H)+。
The structure of the compound 7 obtained is shown below:
Figure BDA0002256984460000232
synthesis of compound 8:
a100 ml reaction flask was charged with intermediate I-4(5.00g, 9.02mmol), N-phenyl- [1,1',4',1 "-terphenyl]-4-amine (2.90g, 9.02mmol), tris (dibenzylideneacetone) dipalladium (0.08g, 0.09mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl (0.07g, 0.18mmol), sodium tert-butoxide (1.30g, 13.53mmol) and toluene solvent (50mL), warmed to 110 ℃ under nitrogen, heated under reflux and stirred for 3 h. After the reaction solution was cooled to room temperature, the reaction solution was extracted with dichloromethane and water, the organic layer was dried over anhydrous magnesium sulfate and filtered, after which the filtrate was passed through a short silica gel column, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization using a dichloromethane/n-heptane system to obtain compound 8(5.02g, yield: 70%). The mass spectrum is as follows: 795.0 (m/z)M+H)+。
The structure of the resulting compound 8 is shown below:
Figure BDA0002256984460000241
synthesis of compound 9:
compound 9 was synthesized in a similar manner to the synthesis of compound 1 except that 2-bromobiphenyl (12.36g, 54.67mmol) was used instead of bromobenzene in reaction formula 1, which was the intermediate I-1 prepared, to give compound 9(3.99g, yield: 70%). The mass spectrum is as follows: m/z 718.9(M + H)+。
The structure of the compound 9 obtained is shown below:
Figure BDA0002256984460000242
in one embodiment, compound X, wherein X is 10, 11, 12 or 13, is synthesized in a manner similar to the synthesis of compound 3, except that compound SM-B is used in place of bromobenzene in reaction formula 1 for the preparation of intermediate I-1, for example compound SM-B is 2-bromobiphenyl, 1-bromonaphthalene, 2-bromonaphthalene or 4-bromop-terphenyl, and each compound SM-B produces the only corresponding compound X. For example, the synthesis process is shown in the formula 2, where the formula 2 is:
Figure BDA0002256984460000251
synthesis of compound 10:
compound 10 was synthesized in a similar manner to the synthesis of compound 3 except that 1-bromonaphthalene (15.09g, 54.67mmol) was used instead of bromobenzene to give compound 10(4.57g, yield: 72%). The mass spectrum is as follows: 768.9(M + H) M/z+。
The structure of the resulting compound 10 is shown below:
Figure BDA0002256984460000252
synthesis of compound 11:
compound 11 was synthesized in a similar manner to the synthesis of compound 3 except that 2-bromonaphthalene (15.09g, 54.67mmol) was used instead of bromobenzene to give compound 11(4.44g, yield: 70%). The mass spectrum is as follows: 768.9(M + H) M/z+。
The structure of the resulting compound 11 is shown below:
Figure BDA0002256984460000261
synthesis of compound 12:
compound 12 was synthesized in a similar manner to the synthesis of compound 3 except that 2-bromobiphenyl (12.36g, 54.67mmol) was used instead of bromobenzene to give compound 12(4.47g, yield: 71%). The mass spectrum is as follows: m/z 795.0(M + H)+。
The structure of the resulting compound 12 is shown below:
Figure BDA0002256984460000262
synthesis of compound 13:
compound 13 was synthesized in a similar manner to the synthesis of compound 3 except that 4-bromo-p-terphenyl (20.51g, 54.67mmol) was used instead of bromobenzene to give compound 13(4.37g, yield: 71%). The mass spectrum is as follows: m/z 871.1(M + H)+。
The structure of the resulting compound 13 is shown below:
Figure BDA0002256984460000271
synthesis of compound 14:
compound 14 was synthesized in a similar manner to that of compound 1, except thatSynthesis of intermediate I-3 Using 4-bromobenzeneboronic acid (43.03g, 214.31mmol) in place of m-bromobenzeneboronic acid, Compound 14(4.17g, yield: 75%) was obtained. The mass spectrum is as follows: m/z 642.8(M + H)+。
The structure of the resulting compound 14 is shown below:
Figure BDA0002256984460000272
synthesis of compound 15:
compound 15 was synthesized in a similar manner to the synthesis of compound 6 except that 4-bromobenzeneboronic acid (43.03g, 214.31mmol) was used in the synthesis of intermediate I-3 instead of m-bromobenzeneboronic acid to give compound 15(4.61g, yield: 74%). The mass spectrum is as follows: m/z 692.8(M + H)+。
The structure of the resulting compound 15 is shown below:
Figure BDA0002256984460000281
synthesis of compound 16:
compound 16 was synthesized in a similar manner to that of compound 3 except that 4-bromobenzeneboronic acid (43.03g, 214.31mmol) was used in the synthesis of intermediate I-3 instead of m-bromobenzeneboronic acid to give compound 16(4.60g, yield: 71%). The mass spectrum is as follows: m/z 718.9(M + H)+。
The structure of the resulting compound 16 is shown below:
Figure BDA0002256984460000282
synthesis of compound 17:
compound 17 was synthesized in a similar manner to that of compound 5 except that 4-bromobenzeneboronic acid (43.03g, 214.31mmol) was used in the synthesis of intermediate I-3 instead of m-bromobenzeneboronic acid to give compound 17(5.00g, yield: 70%). The mass spectrum is as follows: m/z 795.0(M + H)+。
The structure of the resulting compound 17 is shown below:
Figure BDA0002256984460000291
synthesis of compound 18:
compound 18 was synthesized in a similar manner to the synthesis of compound 2 except that 4-bromobenzeneboronic acid (43.03g, 214.31mmol) was used in the synthesis of intermediate I-3 instead of m-bromobenzeneboronic acid to give compound 18(4.92g, yield: 71%). The mass spectrum is as follows: 768.9(M + H) M/z+。
The structure of the resulting compound 18 is shown below:
Figure BDA0002256984460000292
preparation of intermediate II-1:
1-bromo-2-fluoro-3-iodobenzene (10.00g, 33.23mmol), 2-methoxyphenylboronic acid (5.05g, 33.23mmol), tetrakis (triphenylphosphine) palladium (1.92g, 1.66mmol), potassium carbonate (9.18g, 66.46mmol), tetrabutylammonium chloride (0.38g, 1.66mmol), toluene (30mL), ethanol (16mL), and deionized water (8mL) were added to a round bottom flask, warmed to 78 deg.F under nitrogen, stirred for 12 hours, the reaction was cooled to room temperature, toluene (200mL) was added for extraction, the organic phases were combined, dried over anhydrous magnesium sulfate and filtered, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica gel using n-heptane as a mobile phase, followed by purification by recrystallization from a dichloromethane/ethyl acetate system to give intermediate II-1(14.48g, yield: 75%).
Preparation of intermediate II-2:
intermediate II-1(14.48g, 51.51mmol) and dichloromethane (150 ml) were added to a round-bottom flask and stirred at room temperature under nitrogen for 30 min. Then cooled to 0, and then a solution of boron tribromide in methylene chloride (19.35g, 77.26mmol) was added dropwise thereto, and after keeping at low temperature for 20min, the mixture was warmed to room temperature and stirred for 3 h. After the reaction was completed, the temperature was reduced to-78 deg.C, and 20ml of methanol was added for deactivation. Dichloromethane (200mL) was added for extraction, the organic phases were combined, dried over anhydrous magnesium sulfate and filtered, and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography using n-heptane as a mobile phase to obtain intermediate II-2(9.63g, yield: 70%).
Preparation of intermediate II-3:
intermediate II-2(9.63g, 36.05mmol), sodium hydroxide (2.88g, 72.10mmol), N-methylpyrrolidone (2.08g, 1.80mmol) were charged into a round-bottomed flask, heated to reflux and stirred for 3 hours, the reaction solution was cooled to room temperature, methylene chloride (200mL) was added for extraction, the organic phases were combined, dried over anhydrous magnesium sulfate and filtered, the solvent was removed under reduced pressure, the resulting crude product was purified by silica gel column chromatography using methylene chloride as a mobile phase, and concentrated to dryness to obtain intermediate II-3(6.33g, yield: 71%).
Preparation of intermediate II-4:
intermediate II-3(6.33g, 25.61mmol) was added dropwise to a 250ml three-necked flask containing THF (50ml) in-78, n-butyllithium (1.72g, 26.89mmol) was added dropwise, and after the addition was complete, incubation was continued for 1h, then trimethyl borate (3.99g, 38.42mmol) was added dropwise, and after 1h of incubation was continued, the mixture was warmed to room temperature and stirred overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutrality, followed by filtration to give a white crude product, which was slurried with n-heptane to give intermediate II-4(3.80g, yield: 70%).
For example, intermediate II-4 is obtained by reaction 3, reaction 3 being:
Figure BDA0002256984460000301
preparation of intermediate II-5:
intermediate II-5 was synthesized in a similar manner to the synthesis and purification of intermediate II-4 except that 2-iodo-4-bromofluorobenzene (10.00g, 33.23mmol) was used instead of 1-bromo-2-fluoro-3-iodobenzene to give intermediate II-5(3.96g, yield: 73%).
Preparation of intermediate II-6:
intermediate II-6 was synthesized in a similar manner to the synthesis and purification of intermediate II-4 except that 2-bromo-6-fluoroiodobenzene (10.00g, 33.23mmol) was used instead of 1-bromo-2-fluoro-3 iodobenzene to give intermediate II-6(4.01g, yield: 73%).
Synthesis of compound 19:
compound 19 was synthesized in a similar manner to the synthesis of Compound 1 except that intermediate II-4(3.80g, 0.018mmol) was used in place of compound SM1 to give compound 19(4.05g, yield: 73%). M/z 642.8(M + H)+。
The structure of the resulting compound 19 is shown below:
Figure BDA0002256984460000311
synthesis of compound 20:
compound 20 was synthesized in a similar manner to the synthesis and purification of Compound 1 except that intermediate II-5(3.96g, 0.019mmol) was used in place of compound SM1 to give Compound 20(3.99g, yield: 72%). M/z 642.80(M + H)+。
The structure of the resulting compound 20 is shown below:
Figure BDA0002256984460000312
synthesis of compound 21:
compound 21 was synthesized in a similar manner to the synthesis and purification of Compound 1 except that intermediate II-6(4.01g, 0.019mmol) was used in place of compound SM1 to give Compound 21(3.93g, yield: 71%). M/z 642.8(M + H)+。
The structure of the resulting compound 21 is shown below:
Figure BDA0002256984460000313
synthesis of compound 22:
in a similar manner to the Synthesis and purification of Compound 1Compound 22 was synthesized except that 2,4, 6-trichloropyrimidine (10.0g, 54.97mmol) was used in place of 2,4, 6-trichloro-1, 3, 5-triazine to give compound 22(3.87g, yield: 70%). M/z 641.8(M + H)+。
The structure of the resulting compound 22 is shown below:
Figure BDA0002256984460000321
preparation of intermediate I-5:
A1L reaction flask was charged with intermediate I-2(76.68g, 214.30mmol), p-bromophenylboronic acid (43.03g, 214.31mmol), and 620ml of 1, 4-dioxane, and stirred at 60 ℃ under a nitrogen atmosphere, and tetrakis (triphenyl) phosphine palladium (12.38g, 10.72mmol) and 50ml of an aqueous solution of potassium carbonate (59.24g, 428.62mmol) were added, and stirred at elevated temperature under reflux overnight. The reaction solution was cooled to room temperature, and the solid was washed with methanol and ultrapure water and recrystallized from toluene to obtain intermediate I-5(76.8g, yield 75%).
Preparation of intermediate I-6:
A1L reaction flask was charged with (76.8g, 161.0mmol) of intermediate I-5, 2, 7-dibromo-9-phenylcarbazole (64.57g, 161.0mmol) and 500ml of 1, 4-dioxane, and stirred at 60 ℃ under a nitrogen atmosphere, and tetrakis (triphenyl) phosphine palladium (9.30g, 8.05mmol) and 100ml of an aqueous solution of potassium carbonate (66.65g, 483.0mmol) were added, and stirred at reflux at elevated temperature overnight. The reaction solution was cooled to room temperature, and the solid was washed with methanol and ultrapure water and recrystallized from toluene to obtain intermediate I-6(89.16g, yield 77%).
In one embodiment, compound X, wherein X is 103, 104, 105, is synthesized in a manner similar to the synthesis of compound 1, except that the compound p-bromobenzeneboronic acid is used instead of m-bromobenzeneboronic acid, which is used to prepare intermediate I-3 in equation 1, and the compound 2, 7-dibromo-9-phenylcarbazole is used instead of p-bromobenzeneboronic acid, which is used to prepare intermediate I-4 in equation 1. The compound SM-A is diphenylamine, N-phenyl-4-benzidine, N-phenyl-2-naphthylamine, and it produces the compound X which corresponds exclusively thereto. For example, the synthesis process is shown in the formula 4, wherein the formula 4 is:
Figure BDA0002256984460000331
synthesis of compound 23:
a100 mL reaction flask was charged with intermediate I-6(5.00g, 6.94mmol), diphenylamine (1.17g, 6.94mmol), tris (dibenzylideneacetone) dipalladium (0.06g, 0.06mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl (0.07g, 0.14mmol), sodium tert-butoxide (2.0g, 20.84mmol) and toluene solvent (50mL), warmed to 110 deg.f under nitrogen protection, heated under reflux and stirred for 3 h. After the reaction solution was cooled to room temperature, the reaction solution was extracted with dichloromethane and water, the organic layer was dried over anhydrous magnesium sulfate and filtered, and after filtration, the filtrate was passed through a short silica gel column, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization using a dichloromethane/n-heptane system to obtain compound 23(4.30g, yield: 76%). The mass spectrum is as follows: m/z 807.3(M + H)+。
The structure of the resulting compound 23 is shown below:
Figure BDA0002256984460000332
synthesis of compound 24:
compound 24 was synthesized in a similar manner to that of compound 23 except that N-phenyl-4-benzidine (1.7g, 6.94mmol) was used instead of diphenylamine to give compound 24(4.51g, yield: 73%). The mass spectrum is as follows: m/z 883.3(M + H)+。
The structure of the resulting compound 24 is shown below:
Figure BDA0002256984460000341
synthesis of compound 25:
compound 25 was synthesized in a similar manner to that of compound 23, except that N-phenyl-2-naphthylamine (1.52 g) was used6.94mmol) instead of diphenylamine gave compound 25(4.3g, yield: 72%). The mass spectrum is as follows: m/z 857.3(M + H)+。
The structure of the resulting compound 25 is shown below:
Figure BDA0002256984460000342
the present application also provides an electronic component, as shown in fig. 1, comprising an anode 1 and a cathode 5 oppositely arranged, and a functional layer 3 arranged between the anode 1 and the cathode 5, wherein the functional layer 3 comprises the compound provided in any one of the above embodiments.
The anode 1 is a material that facilitates hole injection into the functional layer 3, and has a large work function. For example, the anode 1 is made of metal, alloy, metal oxide, etc., for example, it may be nickel, platinum, vanadium, chromium, copper, zinc, gold, or 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), and of course, the anode 1 material is not limited thereto but may be other materials, which are not listed here. Preferably, the anode 1 material is Indium Tin Oxide (ITO).
The cathode 5 is a material that facilitates electron injection into the functional layer 3, the material having a small work function. For example, the cathode 5 material is 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 it may be a multi-layer 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 is aluminum. For example, the electronic element may be an organic electroluminescent device, but of course, other electronic elements may be used, not limited theretoTo be enumerated again.
The compounds of any of the embodiments of the present application can be used to form one or more layers of the functional layer 3 to reduce the operating voltage of electronic components, improve the luminous efficiency, and extend the device lifetime. Specifically, the functional layer 3 includes an electron transport layer 35, and the electron transport layer 35 includes the compound according to any one of the embodiments of the present application. The compound is used as an electron transport material for improving the electron mobility, and further improving the recombination probability of electrons and holes, thereby improving the luminous efficiency.
The functional layer 3 further comprises a light-emitting layer 33 and a hole transport layer 31, wherein: the light-emitting layer 33 is arranged on one side of the electron transport layer 35 close to the anode 1; the hole transport layer 31 is provided on the side of the light-emitting layer 33 remote from the cathode 5. The electronic element includes an anode 1, a hole transport layer 31, a light-emitting layer 33, an electron transport layer 35, and a cathode 5, which are stacked. The compound provided herein is used for the electron transport layer 35 of an electronic element for improving the electronic characteristics of the electronic element, wherein the electronic characteristics may mean that electrons formed in the cathode 5 are easily injected into the light emitting layer and transported in the light emitting layer according to the conduction characteristics of the LUMO level.
Meanwhile, the electronic component of the embodiment of the present application further includes a hole injection layer 2, an electron injection layer 4, an electron blocking layer 32, or a hole blocking layer 34, wherein the hole injection layer 2 is disposed between the anode 1 and the hole transport layer 31; the electron injection layer 4 is provided between the cathode 5 and the electron transport layer 35; the electron blocking layer 32 is provided between the light-emitting layer 33 and the hole transport layer 31; the hole blocking layer 34 is provided between the light-emitting layer 33 and the electron transport layer 35.
In other embodiments, as shown in fig. 2, the electronic component is also a solar cell, which may be, for example, an organic solar cell. The organic electroluminescent device mainly comprises a cathode 400, an anode 200 and a functional layer 300, wherein the functional layer 300 is arranged between the cathode 400 and the anode 200, and the functional layer 300 comprises the compound in any embodiment of the application and is used for improving the transmission rate of excitons. In one embodiment, the functional layer 300 includes an electron transport layer 303, a hole transport layer 301 and a photosensitive active layer 302, the anode 200 is formed on a substrate 100, the anode 200 is a thin film attached to the substrate 100, the hole transport layer 301 is formed on the surface of the anode 200 away from the substrate 100, the photosensitive active layer 302 is formed on the surface of the hole transport layer 301 away from the anode 200, the electron transport layer 303 is formed on the surface of the photosensitive active layer 302 away from the hole transport layer 301, the electron transport layer 303 includes the compound according to any of the embodiments, and the cathode 400 is further formed on the 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 is generated between the cathode 400 and the anode 200 of the solar cell, and a power generation function is realized. In this process, the compound of this application can be arranged in the transmission rate of reinforcing electron among the electron transport layer 303, avoid electron and hole to take place recombination, and then the quantity of multiplicable electron to negative pole 400 transmission, thereby improve solar cell's open circuit voltage, improve photoelectric conversion efficiency, again because the compound of this application accessible dibenzofuran (dibenzothiophene) 2 number position and triazine or pyrimidine are each other and introduce nitrogen heterocycle on the structure of meta position (nonconjugate) or counterpoint, effectively strengthened material electron injection ability, further promote device efficiency and life-span.
The present application further provides an electronic device, which may include the electronic component according to any of the above embodiments, and the beneficial effects and 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, an array substrate, a photovoltaic module, or the like, and of course, other devices may also be used, which are not listed here, for example, it may be a screen of a mobile phone 500, a camera, or a computer, and of course, other devices or apparatuses may also be used, which are not limited here.
Hereinafter, the compound and the electronic device of the present application will be described in detail by examples using an organic electroluminescent device as an example. However, the following examples are merely illustrative of the present application and do not limit the present application.
Production and evaluation examples of organic electroluminescent device
Example 1: fabrication of red organic electroluminescent device
The anode 1 was prepared by the following procedure: the thickness of ITO is set as
Figure BDA0002256984460000362
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 used UV ozone and O2:N2And performing surface treatment by using plasma to increase the work function of the anode 1, and cleaning the surface of the ITO substrate by using an organic solvent to remove impurities and oil stains on the surface of the ITO substrate. It should be noted that the ITO substrate is also cut into other sizes according to actual needs, and the size of the ITO substrate in this application is not particularly limited.
HAT-CN (structural formula shown below) was vacuum-evaporated on an experimental substrate (anode 1) to a thickness of
Figure BDA0002256984460000363
And NPB (structural formula is shown below) is evaporated on the hole injection layer 2 to form a layer having a thickness of
Figure BDA0002256984460000364
The hole transport layer 31.
TCTA (4,4' -tris (carbazol-9-yl) triphenylamine) (structural formula shown below) is vapor-deposited on the hole transport layer 31 to a thickness of
Figure BDA0002256984460000365
The hole assist layer of (1).
Depositing CBP (structural formula shown below) as main body on the hole auxiliary layer, and doping Ir (piq)2(acac) (structural formula below), as per 30: 3 film thickness ratio of
Figure BDA0002256984460000366
The light emitting layer 33 (EML).
The doping on the light-emitting layer 33 is 2: 1 and LiQ (structural formula shown below) as an electron transport layer 35 (ETL);
ytterbium (Yb) of 1nm was vapor-deposited on the electron transport layer 35 as an electron injection layer 4 (EIL);
magnesium (Mg) and silver (Ag) were then mixed at a ratio of 1: 9 is vacuum-evaporated on the electron injection layer 4 to a thickness of
Figure BDA0002256984460000367
The cathode of (1).
Further, the cathode 5 is vapor-deposited to a thickness of
Figure BDA0002256984460000368
CP-1 (structural formula is shown below), an organic capping layer (CPL) is formed, thereby completing the fabrication of the organic light emitting device.
Figure BDA0002256984460000361
Figure BDA0002256984460000371
Examples 2 to 25
Organic electroluminescent devices were fabricated in a similar manner to example 1, except that the compounds shown in table 1 were each used in forming the electron transport layer 35(ETL), and the device performance parameters are detailed in table 1.
Comparative examples 1 to 3
In comparative examples 1 to 3, organic electroluminescent devices were manufactured in a similar manner to example 1, except that compounds a to C were used instead of compound 1 as the electron transport layer 35(ETL), respectively. The structural formulas of the compounds A to C are respectively shown as follows:
Figure BDA0002256984460000372
namely: comparative example 1 preparation of an electron transporting layer using Compound AAs an organic electroluminescent device; comparative example 2 an organic electroluminescent device was fabricated using compound B as an electron transport layer; comparative example 3 an organic electroluminescent device was fabricated using compound C as the electron transport layer. The performance parameters of each prepared device are detailed in Table 1, wherein the voltage, the luminous efficiency, the color coordinate and the external quantum efficiency are 10mA/cm at constant current density2Tested under the condition, the T95 device has the service life of 50mA/cm at a constant current density2And (4) testing.
TABLE 1 device Performance of examples 1-25 and comparative examples 1-3
Figure BDA0002256984460000381
Figure BDA0002256984460000391
As can be seen from table 1, in examples 1 to 25 using compounds 1 to 25 as the Electron Transport Layer (ETL), the operating voltage of the organic electroluminescent device prepared using compounds 1 to 25 as the Electron Transport Layer (ETL) in the present invention was reduced by at least 0.42V, while the luminous efficiency (Cd/a) was improved by at least 20.5%, the lifetime was improved by at least 50h, and the lifetime was improved by at least 34.8%, compared to comparative examples 1,2, and 3 using known compounds a, B, and C. Meanwhile, the current efficiency (Cd/a), External Quantum Efficiency (EQE), and lifetime (T95) were all significantly improved in examples 1 to 25 as compared with the comparative example.
The compound provided by the application can reduce the driving voltage because the nitrogen-containing hexabasic heteroaryl is combined with dibenzofuran and aryl amine, especially the triazine group and pyrimidine group in the nitrogen-containing hexabasic heteroaryl are combined with dibenzofuran and aryl amine, and on one hand, the energy level injection barrier is reduced because the nitrogen-containing hexabasic heteroaryl has a lower LUMO energy level than the existing compound. Meanwhile, the nitrogen-containing hexabasic heteroaryl has a stable structure, is not easy to decompose, and has strong high-temperature resistance, so that the service life is prolonged. In addition, the nitrogen-containing six-membered heteroaryl has higher electron affinity and is easy to accept electrons, and has higher electron mobility. Meanwhile, the benzofuran derivative containing the furan structure has good thermal stability, the aryl amine derivative has lower ionization energy, and the nitrogen atom in the derivative has strong electron donating capability and shows higher hole mobility, so that electrons and holes rapidly move to a recombination region, recombination luminescence is realized, dynamic balance is achieved, and the efficiency of the device is further improved.
Other embodiments of the present application will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the application being indicated by the following claims.

Claims (3)

1. An organic electroluminescent device, comprising an anode and a cathode which are oppositely arranged, and a functional layer which is arranged between the anode and the cathode;
the functional layer comprises an electron transport layer, and the electron transport layer comprises a compound with a structural general formula shown as formula I or formula II:
Figure FDA0003356962310000011
wherein Ar is1Selected from the group formed by:
Figure FDA0003356962310000012
Ar2、Ar3the same or different and each independently selected from the group formed by:
Figure FDA0003356962310000013
2. an organic electroluminescent device, comprising an anode and a cathode which are oppositely arranged, and a functional layer which is arranged between the anode and the cathode;
the functional layer comprises an electron transport layer comprising a compound selected from the group consisting of:
Figure FDA0003356962310000021
Figure FDA0003356962310000031
Figure FDA0003356962310000041
Figure FDA0003356962310000051
Figure FDA0003356962310000061
Figure FDA0003356962310000071
Figure FDA0003356962310000081
3. an electronic device comprising the organic electroluminescent element as claimed in claim 1 or 2.
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