CN116023374A - Heterocyclic compound and application thereof - Google Patents

Heterocyclic compound and application thereof Download PDF

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CN116023374A
CN116023374A CN202310138519.5A CN202310138519A CN116023374A CN 116023374 A CN116023374 A CN 116023374A CN 202310138519 A CN202310138519 A CN 202310138519A CN 116023374 A CN116023374 A CN 116023374A
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冯静
赵利杰
何连贞
唐怡杰
邸庆童
张昊
边坤
刘殿君
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Beijing Bayi Space LCD Technology Co Ltd
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Abstract

The invention relates to the technical field of organic electroluminescent materials, in particular to a heterocyclic compound and application thereof. The structural formula of the heterocyclic compound is shown in a formula (I); the compound shown in the formula (I) provided by the invention has an oxazole ring structure. The compound is applied to an organic electroluminescent element, so that the driving voltage can be obviously reduced, the luminous efficiency can be improved, and the service life can be prolonged;
Figure DDA0004086805340000011

Description

Heterocyclic compound and application thereof
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a heterocyclic compound and application thereof in an organic light-emitting element.
Background
In general, an organic light emitting phenomenon refers to a phenomenon that emits light when electric energy is applied to an organic substance; that is, when an organic layer is disposed between an anode and a cathode, if a voltage is applied between the two electrodes, holes are injected from the anode to the organic layer, and electrons are injected from the cathode to the organic layer; when the injected holes and electrons meet, excitons are formed, and when the excitons transition to a ground state, light and heat are emitted.
In recent years, organic electroluminescent display technology has tended to mature, and some products have entered the market, but in the industrialization process, many problems still remain to be solved. In particular, various organic materials for manufacturing elements, which have carrier injection and transport properties, material electroluminescent properties, service life, color purity, matching between various materials and between various electrodes, and the like, have not been solved; in particular, as the materials applied to the electron transport layer and the hole blocking layer, as the earliest reports on the electron transport material, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and materials for the representative electron transport layer of imidazolyl groups described in CN107573328A, CN107556310A, CN113801066A, CN113429395A, CN113429348A, CN114560872a and the like are given. The structure contains 1,3, 4-oxadiazole groups, which have the ability to transport electrons in terms of functions, but have a problem of low thermal stability when applied to practical elements.
In order to overcome the above-described problems of the conventional techniques and to further improve the characteristics of the organic electroluminescent element, there is a continuing need for the development of a more stable and effective substance that can be used as an electron transporting and hole blocking substance in the organic electroluminescent element.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a heterocyclic compound which can improve the thermal stability of materials and the capability of transporting carriers, and an organic electroluminescent element prepared by the heterocyclic compound can obviously reduce driving voltage, improve luminous efficiency and prolong service life; it is a further object of the present invention to provide the use of the compounds.
Specifically, the invention provides the following technical scheme:
the invention provides a heterocyclic compound, the structural formula of which is shown as the formula (I):
Figure BDA0004086805320000011
wherein,,
Ar 1 selected from the group consisting of substituted and unsubstituted C 2 -C 60 Heteroaryl groups;
L 1 selected from the group consisting of substituted and unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroarylenes;
L 2 、L 3 each independently selected from the group consisting of single bond, substituted or unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroarylenes;
X 1 、X 2 、X 3 Each independently is CR 1 Or N, and x 1 、X 2 、X 3 Wherein the total number of N is 1 or 3;
R 1 selected from hydrogen, deuterium, fluorine, nitrile, nitro, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, substituted or unsubstituted C 1 -C 40 Alkyl, substituted or unsubstituted C 1 -C 40 Alkoxy, substituted or unsubstituted C 2 -C 40 Alkenyl, substituted or unsubstituted C 1 -C 40 Alkylthio, substituted or unsubstituted C 3 -C 40 Cycloalkyl, substituted or unsubstituted C 1 -C 40 Alkyl sulfoxide group, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 6 -C 60 Aryl sulfoxide group, substituted or unsubstituted C 3 -C 40 Silyl, substituted or unsubstituted boron, substituted or unsubstituted amine, substituted or unsubstituted aryl phosphine, substituted or unsubstituted phosphine oxide, or substituted or unsubstituted C 2 -C 60 Heteroaryl groups;
Ar 2 、Ar 3 each independently selected from the group consisting of substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 Heteroaryl groups.
In the present invention, the term "ring" means a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring, which is formed by bonding adjacent groups to each other. The condensed ring means a condensed aliphatic ring, a condensed aromatic ring, a condensed aliphatic heterocyclic ring, a condensed aromatic heterocyclic ring, or a combination thereof.
The heterocyclic compound according to the present invention is represented by the above formula (I), wherein the heterocyclic compound comprises a 1,3, 4-oxadiazole group and a hetero atomHeteroaryl of the nucleus and 3, 5-disubstituted aryl or heteroaryl are substituted by arylene, heteroarylene L 1 And are combined to form a basic framework. The compound represented by the formula (I) of the present invention is electrochemically stable, has excellent electron mobility, has a high glass transition temperature, and has excellent thermal stability, as compared with the conventionally known oxadiazole derivatives. Thus, the heterocyclic compound of the present invention is excellent in electron transporting ability and light emitting property, and therefore can be used as a material for any one of a light emitting layer, an electron transporting layer and a hole blocking layer of an organic electroluminescent element. A material that can be used as any one of the light-emitting layer, the electron-transporting layer, and the electron-transporting auxiliary layer that is stacked over the hole-blocking layer in one step is preferable, and a material that can be used as the electron-transporting layer or the electron-transporting auxiliary layer is more preferable.
Specifically, the compound represented by the formula (I) of the present invention has a higher electron-transporting ability than the aryl oxadiazole derivative having a weak electron-withdrawing group by the heterocyclic compound containing heteroaryl oxadiazole, and can exhibit a relatively high luminous efficiency and a high glass transition temperature. Thus, when the heterocyclic compound represented by the formula (I) of the present invention is used for an organic electroluminescent element, not only excellent thermal stability and carrier transport ability, particularly electron transport ability and light emitting ability, but also reduction in driving voltage of the element, improvement in efficiency, lifetime, and the like can be expected, and excellent efficiency increase due to triplet-triplet amyl fusion effect can be exhibited as a latest electron transport layer material due to high triplet energy level.
In addition, the heterocyclic compound of formula (I) of the present invention is obtained by introducing a plurality of substituents Ar into the basic skeleton 1 、Ar 2 And Ar is a group 3 The HOMO and LUMO energy levels are adjusted according to the kind of substituent, and thus a wide band gap can be provided, and the organic electroluminescent element using such a compound can exhibit the highest electron transport property.
In addition, the heterocyclic compound represented by the formula (I) of the present invention is obtained by introducing various substituents L into the above basic skeleton 1 、L 2 、L 3 In particular aryl and/or heteroaryl groupsAr 2 And Ar is a group 3 The molecular weight of the compound is significantly increased, and the glass transition temperature is increased, whereby the compound can have higher thermal stability than conventional luminescent materials such as a plurality of aryl-linked oxadiazoles. Therefore, the performance and lifetime characteristics of the organic electroluminescent element comprising the compound according to the present invention can be greatly improved. The organic electroluminescent element thus improved in performance and lifetime characteristics can eventually maximize the performance of the full-color organic light-emitting panel.
Preferably, the R 1 Selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, methyl, phenyl, biphenyl, terphenyl, naphthyl, pyridyl, phenanthryl, triphenylenyl, carbazolyl, fluorenyl, dibenzofuranyl, or dibenzothiophenyl.
Aryl groups in the sense of the present invention contain 6 to 60 carbon atoms, heteroaryl groups contain 2 to 60 carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5; the heteroatom is preferably selected from N, O or S. In this case, two or more rings of the heteroaryl group may be attached to each other simply or in a condensed form, or may further include a condensed form with the aryl group. As non-limiting examples of such heteroaryl groups, six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, and the like can be cited; polycyclic rings such as phenoxazolyl, indolizinyl, indolyl, purinyl, quinolinyl, benzothiazolyl, carbazolyl, and the like; 2-furyl, N-imidazolyl, 2-isoxazolyl, 2-pyridyl, 2-pyrimidinyl, and the like.
The condensed ring aryl group used in the present invention means a monovalent functional group obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms, which is a combination of two or more rings. In this case, two or more rings may be attached to each other singly or in a condensed form. As non-limiting examples thereof, there may be mentioned phenanthryl, anthracyl, fluoranthracyl, pyrenyl, triphenylenyl, perylenyl,
Figure BDA0004086805320000021
A base, etc.
Preferably, the method comprisesThe aryl, condensed ring aryl, heteroaryl can be selected from phenyl, naphthyl, anthryl, benzanthraceyl, phenanthryl, pyrenyl, and the like,
Figure BDA0004086805320000022
A group, perylene group, fluoranthenyl group, naphthacene group, pentacene group, benzopyrene group, biphenyl group, terphenyl group, tripolyphenyl group, tetrabiphenyl group, fluorenyl group, spirobifluorenyl group, dihydrophenanthrene group, triphenylene group, dihydropyrenyl group, tetrahydropyrenyl group, cis-or trans-indenofluorenyl group, cis-or trans-indenocarbazolyl group, indolocarbazolyl group, benzofuranocarbazolyl group, benzothiophenocarbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, azadibenzo [ g, ij]Naphtho [2,1,8-cde]Azulene, triindenyl, heterotrimeric indenyl, spirotrimeric indenyl, spiroheterotrimeric indenyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, pyridyl, quinolinyl, isoquinolinyl, acridinyl, phenanthridinyl, benzo [5,6 ]]Quinolinyl, benzo [6,7]Quinolinyl, benzo [7,8]Quinolinyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthaminyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthazolyl, anthracnose oxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthryl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazaanthracenyl, 2, 7-diazapyrenyl, 2, 3-diazapyrenyl, 1, 6-diazapyrenyl, 1, 8-diazapyrenyl, 4,5,9, 10-tetraazaperylene group, pyrazinyl group, phenazinyl group, phenoxazinyl group, phenothiazinyl group, fluorozinyl group, naphthyridinyl group, azacarbazolyl group, benzocarboline group, carboline group, phenanthroline group, 1,2, 3-triazolyl group, 1,2, 4-triazolyl group, benzotriazole group, 1,2, 3-oxadiazolyl group, 1,2, 4-oxadiazolyl group, 1,2, 5-oxadiazolyl group, 1,3, 4-oxadiazolyl group, 1,2, 3-thiadiazolyl group, 1,2,4 -thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, quinazolinyl, benzothiadiazolyl or groups derived from combinations of these systems.
Further, the Ar 2 、Ar 3 Each independently selected from the group consisting of phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthryl, pyrenyl,
Figure BDA0004086805320000032
a group, perylene group, fluoranthenyl group, naphthacene group, pentacene group, benzopyrene group, biphenyl group, terphenyl group, tripolyphenyl group, tetrabiphenyl group, fluorenyl group, spirobifluorenyl group, dihydrophenanthrene group, triphenylene group, dihydropyrenyl group, tetrahydropyrenyl group, cis-or trans-indenofluorenyl group, cis-or trans-indenocarbazolyl group, indolocarbazolyl group, benzofuranocarbazolyl group, benzothiophenocarbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, azadibenzo [ g, ij]Naphtho [2,1,8-cde]Azulene, triindenyl, heterotrimeric indenyl, spirotrimeric indenyl, spiroheterotrimeric indenyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, pyridyl, quinolinyl, isoquinolinyl, acridinyl, phenanthridinyl, benzo [5,6 ] ]Quinolinyl, benzo [6,7]Quinolinyl, benzo [7,8]Quinolinyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthazolyimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthazolyl, anthracnose oxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthryl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazaanthracenyl, 2, 7-diazapyrenyl, 2, 3-diazapyrenyl, 1, 6-diazapyrenyl,1, 8-diazapyrenyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluoroerythronyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, carbolinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazolyl, 1,2, 3-tetrazolyl, 1,3, 4-triazinyl, 4-tetrazolyl, a group of these groups, a group of groups, a quinazoline group, a combination of these groups, a quinazoline group, a group of groups, a combination of groups, a quinazoline group, a combination of groups.
In the heterocyclic compound of formula (I) of the present invention, ar 1 Can be selected from the group consisting of commonly known electron withdrawing groups, in which case Ar is as described above 1 Preferably selected from the group consisting of the groups shown in the following II-1 to II-13:
Figure BDA0004086805320000031
wherein,,
Z 1 、Z 2 each independently selected from the group consisting of hydrogen, deuterium, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 40 Alkyl, C 2 -C 40 Alkenyl, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy, C 3 -C 40 Naphthene radical, C 3 -C 40 Cycloalkenyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Aryl sulfide group, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 Heteroaryl groups;
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
T 1 represent O, S or NAr';
ar' is selected from C 1 ～C 40 Alkyl, C of (2) 1 ～C 40 Heteroalkyl of (C) 3 ～C 40 Cycloalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 Heteroaryl groups; preferably, ar' is methyl, ethyl, phenyl, biphenyl or naphthyl;
Figure BDA0004086805320000041
Ar is represented by 1 A linkage to 1,3, 4-oxadiazole; />
The groups represented by the above formulas II-1 to II-13 may each be independently selected from deuterium, halogen atom, nitrile group, nitro group, C 1 -C 40 Alkyl, C 2 -C 40 Alkenyl, C 2 -C 40 Alkynyl, C 3 -C 40 Cycloalkyl, C 3 -C 40 Heterocycloalkyl, C 6 -C 60 Aryl and C 2 -C 60 Heteroaryl, C 1 -C 40 Alkoxy, C 6 -C 60 Aryloxy, C 1 -C 40 Alkylsilyl, C 6 -C 60 Arylsilyl, C 1 -C 40 Alkyl boron group, C 6 -C 60 Arylboron, C 6 -C 60 Aryl phosphino, C 1 -C 60 Aryl phosphine oxide group and C 6 -C 60 More than one substituent in the group consisting of arylamine groups, in this case, when the substituents are plural, it is preferable that the plural substituents are the same or different from each other.
In the heterocyclic compound of formula (I) of the present invention, L 1 To contain the above impuritiesAryl-containing 1,3, 4-oxadiazole derivatives and Ar-containing compounds as described above 2 And Ar is a group 3 The aryl or heteroaryl linked functional group of (2) may be selected from the group consisting of C 6 -C 60 Arylene and C of (2) 2 -C 60 In this case, preferably, the group of heteroarylenes is the group L 1 Selected from the group consisting of the groups indicated below under III-1 to III-25. L (L) 2 、L 3 As a mixture with Ar 2 And Ar is a group 3 The linking group of (2) may be selected from single bond, C 6 -C 60 Arylene and C of (2) 2 -C 60 In this case, preferably, the group of heteroarylenes is the group L 2 、L 3 Selected from the group consisting of single bonds or groups indicated below as III-1 to III-25. The groups shown in III-1 to III-25 are:
Figure BDA0004086805320000042
Wherein X is selected from O, S, se, CR 2 R 3 、SiR 2 R 3 Or NAr 3 ；
Z 11 、Z 12 、Z 13 、Z 14 Each independently selected from the group consisting of hydrogen, deuterium, halogen atoms, hydroxyl, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 60 Alkyl, C of (2) 2 -C 60 Alkenyl, C 2 -C 60 Alkynyl, C 1 -C 60 Alkoxy, C 3 -C 60 Is C 3 -C 60 Cyclic olefin group, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Aryl sulfide group, or substituted or unsubstituted C 2 -C 60 Heteroaryl groups;
y1 represents an integer of 1 to 4; y2 represents an integer of 1 to 6; y3 represents an integer of 1 to 3; y4 represents an integer of 1 to 5; y5 represents an integer of 1 or 2;
R 2 、R 3 each independently selected from the group consisting of C 1 -C 60 Alkyl, C of (2) 1 -C 60 Is optionally substituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 Heteroaryl group, R 2 And R is 3 Optionally joined or fused to form one or more additional substituted or unsubstituted rings with or without one or more heteroatoms N, P, B, O or S in the formed ring; preferably, R 2 、R 3 Methyl, phenyl or fluorenyl;
Ar 3 selected from C 1 -C 60 Alkyl, C of (2) 1 -C 60 Heteroalkyl of (C) 3 -C 60 Cycloalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 Heteroaryl groups; preferably Ar 3 Methyl, ethyl, phenyl, biphenyl or naphthyl;
wherein the dotted line represents the linking site of the group, and the binding site of the groups represented by the above formulas III-1 to III-25 is not limited, and may be any of ortho-, meta-, and para-ones. L as described above 2 、L 3 Can be independently selected from deuterium, halogen atom, nitrile group, C 1 -C 40 Alkyl, C 6 -C 60 Aryl and C 2 -C 60 When the substituent is plural, it is preferable that the plural substituents are the same or different from each other.
In the present invention, the term "substituted or unsubstituted" means that the compound is selected from hydrogen, deuterium, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group or carboxylate thereof, sulfonic acid group or sulfonate thereof, phosphoric acid group or phosphate thereof, and C 1 -C 40 Alkyl, C 2 -C 40 Alkenyl, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy, C 3 -C 40 Cycloalkyl, C 3 -C 40 Cycloalkenyl, C 6 -C 60 Aryl, C 6 -C 60 Aryloxy, C 6 -C 60 Aryl sulfide group and C 2 -C 60 More than 1 substituent in the heterocyclic aryl group is substituted or unsubstituted, or a substituent which is formed by connecting more than 2 substituents in the above exemplified substituents is substituted or unsubstituted.
Alkyl radicals in the sense of the present invention contain 1 to 40 carbon atoms and in which the individual hydrogen atoms or-CH 2 -linear alkyl groups or alkyl groups with branches, the groups of which may also be substituted; alkenyl or alkynyl groups contain at least two carbon atoms, and alkyl, alkenyl or alkynyl groups are preferably considered to mean, by way of non-limiting example, the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.
Alkoxy is preferably an alkoxy group having 1 to 40 carbon atoms, which is taken to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octoxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2, 2-trifluoroethoxy.
Heteroalkyl is preferably an alkyl radical having from 1 to 40 carbon atoms, meaning in which the hydrogen atom or-CH is alone 2 Groups substituted by oxygen, sulfur, halogen atoms, examples being, but not limited to, alkoxy, alkylthio, fluoroalkoxy, fluoroalkylthio, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, n-propylthioIsopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, trifluoromethylthio, trifluoromethoxy, pentafluoroethoxy, pentafluoroethylthio, 2-trifluoroethoxy, 2-trifluoroethylthio, ethyleneoxy, ethylenethio, propyleneoxy, propylenethio, butylenethio, butyleneoxy, pentyleneoxy, cyclopentylenethio, hexeneoxy, hexenethio, cyclohexenyloxy, cyclohexene thio, ethynyloxy, ethynylthio, propynyloxy, propynylthio, butynyloxy, butynylthio, pentynyloxy, pentynylthio, hexynyloxy, hexynylthio.
In general, cycloalkyl, cycloalkenyl groups according to the invention may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, wherein one or more-CH 2 The groups may be replaced by the groups described above; in addition, one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups.
The heterocycloalkyl group used in the present invention means a monovalent functional group obtained by removing one hydrogen atom from a non-aromatic hydrocarbon having a atomic number of 3 to 40. At this time, one or more carbons, preferably 1 to 3 carbons, in the ring are substituted with a heteroatom such as N, O or s. As non-limiting examples thereof, tetrahydrofuran, tetrahydrothiophene, morpholine, piperazine, and the like are given.
As the arylamine group used in the present invention, an arylamine group refers to an amine substituted with an aryl group having 6 to 60 carbon atoms, and as non-limiting examples of the arylamine group, there are a diphenylamino group, an N-phenyl-1-naphthylamine group, an N- (1-naphthyl) -2-naphthylamine group and the like. The heteroarylamino group means an amine substituted with an aryl group having 6 to 60 carbon atoms and a heteroaryl group having 2 to 60 carbon atoms, and as non-limiting examples of the heteroarylamino group, there are N-phenylpyridine-3-amino, N- ([ 1,1 '-biphenyl ] -4-yl) dibenzo [ b, d ] furan-2-amino, N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluorene-2-amino, and the like.
Alkoxy as used herein refers to a monovalent functional group represented by RO-, R is an alkyl group having 1 to 40 carbon atoms, and may include a straight chain, branched chain, or cyclic structure. Non-limiting examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, cyclopentoxy, cyclohexyloxy, and the like.
The aryloxy group used in the present invention means a monovalent functional group represented by R 'O-and R' is an aryl group having 6 to 60 carbon atoms. As non-limiting examples of such aryloxy groups, there are phenoxy, naphthoxy, biphenyloxy, and the like.
The alkylsilyl group used in the present invention means a silyl group substituted with an alkyl group having 1 to 40 carbon atoms, and the number of carbon atoms constituting the alkylsilyl group is at least 3, and as non-limiting examples of the alkylsilyl group, there are trimethylsilyl group, triethylsilyl group and the like. Arylsilyl refers to silyl groups substituted with aryl groups having from 6 to 60 carbon atoms.
The arylphosphorus group used in the present invention means a diarylphosphorus group substituted with an aryl group having 6 to 60 carbon atoms, and as non-limiting examples of the arylphosphorus group, there are diphenylphosphorus group, bis (4-trimethylsilylbenzene) phosphorus group and the like. The phosphorus atom of the aryl phosphorus oxide group is the diaryl phosphorus group is oxidized to the highest valence state.
The arylboron group used in the present invention means a diarylboroyl group substituted with an aryl group having 6 to 60 carbon atoms, and as non-limiting examples of the arylboron group, there are diphenyl boron group, bis (2, 4, 6-trimethylbenzene) boron group and the like. The alkylboryl group means a dialkylboryl group substituted with an alkyl group having 1 to 40 carbon atoms, and as non-limiting examples of the alkylboryl group, there are di-t-butylboryl group, diisobutylboryl group and the like.
Preferably, the heterocyclic compound may be selected from compounds represented by the following formulas J475 to J663:
Figure BDA0004086805320000061
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Figure BDA0004086805320000071
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Figure BDA0004086805320000081
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Figure BDA0004086805320000091
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Figure BDA0004086805320000101
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Figure BDA0004086805320000111
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Figure BDA0004086805320000121
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Figure BDA0004086805320000131
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Figure BDA0004086805320000141
the invention also provides a preparation method of the heterocyclic compound, which is shown in scheme 1:
in the case of scheme 1, the method comprises,
Figure BDA0004086805320000142
in scheme 1, the symbols used are as defined in formula (I) and Y is Cl, br, I or OTf;
the raw materials for synthesizing the compound shown in the formula (I) can be purchased through commercial paths, and the method principles, the operation process, the conventional post-treatment, the column purification, the recrystallization purification and other means are well known to the synthesis personnel in the field, so that the synthesis process can be completely realized to obtain the target product.
Specifically, it isI) Is composed of Ar containing aldehyde group 1 Carrying out condensation reaction with hydrazide to prepare a 1,3, 4-oxadiazole intermediate s1; preparing boric acid or a pinacol borate intermediate S2 from the intermediate S1 containing halogen atoms and pinacol borate or boric acid ester; boric acid or pinacol borate intermediate S2 and containing Ar 2 And Ar is a group 3 The compound of the present invention is prepared by SUZUKI coupling reaction of halogenated aryl or halogenated heteroaryl S3. Intermediate S3 is prepared by palladium-catalyzed or base-catalyzed coupling reactions.
The palladium catalyst which can be used for the palladium-catalyzed coupling reaction may be selected from: pd (P- t Bu 3 ) 2 、Pd(PPh 3 ) 4 、Pd2(dba) 3 、Pd 2 (dba) 3 CHCl 3 、PdCl 2 (PPh 3 ) 2 、PdCl 2 (CH 3 CN) 2 、Pd(OAc) 2 、Pd(acac) 2 、Pd/C、PdCl 2 、[Pd(allyl)C1] 2 Etc., or a mixture of two or more thereof.
In addition, the base used for palladium-catalyzed or base-catalyzed coupling reactions may be selected from: sodium tert-butoxide, potassium tert-butoxide, sodium hydride, lithium hydride, sodium tert-amyl alcohol, sodium ethoxide, sodium methoxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium, potassium hydride, triethylamine, cesium fluoride, and the like, and mixtures of one or two or more thereof.
The coupling reaction may be carried out in an organic solvent, wherein the organic solvent may be selected from the group consisting of: ether solvents such as diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, ethylene glycol diethyl ether, ethylene glycol methyl ether, diethylene glycol diethyl ether, and anisole, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, chlorobenzene, dichlorobenzene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane, and the like, and a mixture of one or more kinds of them may be used.
The invention also provides an organic electroluminescent material, which comprises the heterocyclic compound; the organic electroluminescent material comprising the heterocyclic compound of the present invention has a carrier transporting ability.
The invention also provides application of the heterocyclic compound in preparation of an organic electroluminescent element.
The present invention also provides an organic electroluminescent element comprising: a first electrode, a second electrode, a capping layer, and one or more organic layers disposed between the first electrode and the second electrode; the material of at least one of the organic layer or the capping layer includes the heterocyclic compound described above.
The organic electroluminescent element comprises a cathode, an anode and at least one light emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, exciton-blocking layers, electron-blocking layers and/or charge-generating layers. An intermediate layer having, for example, an exciton blocking function can likewise be introduced between the two light-emitting layers. It should be noted, however, that not every one of these layers need be present. The organic electroluminescent device described herein may comprise one light emitting layer, or it may comprise a plurality of light emitting layers. That is, a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particularly preferred is a system with three light-emitting layers, wherein the three layers can display blue, green and red light emission. If more than one light-emitting layer is present, at least one of these layers comprises the heterocyclic compound of the present invention according to the present invention.
Further, the organic electroluminescent element according to the present invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light emitting layer is directly adjacent to the electron blocking layer or hole transport layer or anode and/or the light emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode.
In the other layers of the organic electroluminescent element according to the invention, in particular in the hole injection and hole transport layers and in the electron injection and electron transport layers, all materials can be used in the manner generally used according to the prior art. A person of ordinary skill in the art will thus be able to use all materials known in relation to organic electroluminescent elements in combination with the light-emitting layer according to the invention without inventive effort.
Furthermore, preference is given to organic electroluminescent elements in which one or more layers are applied by means of a sublimation process, wherein the sublimation process is carried out in a vacuum at a temperature of less than 10 -5 Pa, preferably below 10 -6 The material is applied by vapor deposition at an initial pressure of Pa. However, the initial pressure may also be even lower, for example below 10 -7 Pa。
Preference is likewise given to organic electroluminescent elements in which one or more layers are applied by means of an organic vapor deposition method or by means of carrier gas sublimation, where at 10 -5 The material is applied at a pressure between Pa and 1 Pa. A particular example of this method is an organic vapor jet printing method, wherein the material is applied directly through a nozzle and is thus structured.
Furthermore, organic electroluminescent elements are preferred, from which one or more layers are produced, for example by spin coating, or by means of any desired printing method, for example screen printing, flexography, lithography, photoinitiated thermal imaging, thermal transfer, inkjet printing or nozzle printing. Soluble compounds, for example, are obtained by appropriate substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, a hybrid method is possible, in which one or more layers are applied, for example from a solution, and one or more further layers are applied by vapor deposition.
These methods are generally known to those of ordinary skill in the art and they can be applied to the organic electroluminescent element comprising the compound according to the present invention without inventive effort.
The invention therefore also relates to a method for manufacturing an organic electroluminescent element according to the invention, at least one layer being applied by means of a sublimation method, and/or characterized in that at least one layer is applied by means of an organic vapour deposition method or by means of carrier gas sublimation, and/or in that at least one layer is applied from solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to heterocyclic compounds comprising at least one of the above-indicated invention. The same preferable cases as indicated above with respect to the organic electroluminescent element apply to the compound of the present invention. In particular, it may be preferable to contain other compounds in addition to the heterocyclic compound. Treatment of the heterocyclic compounds of the present invention from the liquid phase, for example by spin coating or by printing methods, requires treatment of the formulations of the compounds of the present invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchyl ketone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylbenzene, 3, 5-dimethylbenzene, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1-bis (3, 4-dimethylphenyl) ethane, or mixtures of these solvents.
Preferably, the organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, or an electron blocking layer.
Further, the light-emitting layer, the electron-transporting layer, the electron-injecting layer, or the hole-blocking layer contains the heterocyclic compound of the present invention.
The invention also provides a consumer product comprising the organic electroluminescent element.
In addition, unless otherwise specified, all raw materials used in the present invention are commercially available, and any ranges recited in the present invention include any numerical value between the end values and any sub-range constituted by any numerical value between the end values or any numerical value between the end values.
The beneficial effects obtained by the invention are as follows:
the heterocyclic compound represented by formula (I) provided by the invention can be applied to an organic layer of an organic electroluminescent element due to excellent electron mobility, thermal stability and luminescence characteristics. In particular, when the heterocyclic compound represented by the formula (I) of the present invention is used for an electron transport layer and an electron transport auxiliary layer, an organic electroluminescent element having a lower driving voltage, higher efficiency and longer lifetime than conventional electron transport materials can be produced, and further, a full-color display panel having improved performance and lifetime can be produced.
Drawings
Fig. 1 shows a schematic diagram of an organic light emitting device 100. The illustrations are not necessarily drawn to scale. The device 100 may include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light emitting layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, a cathode 110, and a capping layer (CPL) 111. The device 100 may be fabricated by sequentially depositing the layers described.
Fig. 2 shows a schematic diagram of an organic light emitting device 200 with two light emitting layers. The device includes a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first emissive layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second emissive layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. The device 200 may be prepared by sequentially depositing the layers described. Because the most common OLED device has one light emitting layer, and device 200 has a first light emitting layer and a second light emitting layer, the light emitting peaks of the first and second light emitting layers may be overlapping or cross-overlapping or non-overlapping. In the corresponding layers of device 200, materials similar to those described with respect to device 100 may be used. Fig. 2 provides one example of how some layers may be added from the structure of device 100.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more; the orientation or positional relationship indicated by the terms "upper", "lower", etc. are based on the orientation or positional relationship shown in the drawings, are merely for convenience of description and to simplify the description, and are not indicative or implying that the apparatus or elements in question must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The experimental materials and related equipment used in the examples below, unless otherwise specified, are all commercially available, and the percentages, such as the percentages without otherwise specified, are all mass percentages.
The following examples are examples of the test apparatus and method for testing the performance of OLED materials and devices as follows:
OLED element performance detection conditions:
luminance and chromaticity coordinates: testing using a spectrum scanner PhotoResearchPr-715;
current density and lighting voltage: testing using a digital source table Keithley 2420;
Power efficiency: NEWPORT 1931-C test was used.
Example 1
A process for the preparation of compound J633 comprising the steps of:
the first step: preparation of intermediate Int-1
Figure BDA0004086805320000161
Under the protection of nitrogen, 20.0mmol of benzoxazole-2-formaldehyde is dissolved in 60mL of dry THF, 20.0mmol of p-bromobenzoyl hydrazine is added, the mixture is heated to reflux and stirred for reaction for 2 hours, the mixture is concentrated to dryness under reduced pressure, the residue is dissolved in 50mL of dimethyl sulfoxide, 24.0mmol of iodine and 60.0mmol of anhydrous potassium carbonate are added, the mixture is heated to 130 ℃ and stirred for reaction for 1 hour, the mixture is cooled to room temperature, the reaction solution is poured into 150mL of ice water and filtered, and filter cakes are washed with water and methanol to obtain a compound Int-1 as a white solid with the yield of 85 percent.
And a second step of: preparation of intermediate Int-2
Figure BDA0004086805320000162
Under the protection of nitrogen, 20.0mmol of Int-1 is dissolved in 60mL of dry DMF, 24.0mmol of pinacol biborate, 30.0mmol of anhydrous potassium acetate and 0.2mmol of PdCl are added 2 (dppf) and 2.0mmol of cuprous iodide, heating to 90 ℃, stirring and reacting for 12 hours, cooling to room temperature, pouring the reaction solution into 120mL of water, filtering, washing a filter cake with water, drying, separating and purifying by a silica gel column to obtain white solid, and obtaining the yield: 82%.
And a third step of: preparation of Compound J633
Figure BDA0004086805320000171
Under the protection of nitrogen, 12.0mmol of intermediate Int-2 (reactant 1), 10.0mmol of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (reactant 2), 36.0mmol of anhydrous sodium carbonate and 40mL of toluene are mixed, then 0.01mmol of Pd132 catalyst, 20mL of ethanol and 20mL of water are added, the mixture is heated to reflux and stirred for reaction for 12 hours, cooled to room temperature, 50mL of water is added for dilution, dichloromethane extraction is used, an organic phase is collected, dried, filtered, filtrate is concentrated to dryness under reduced pressure, and the compound J633, white solid, yield 77 percent, MS (MALDI-TOF) are obtained through separation and purification by a silica gel column: m/z=571.1896 [ m+h ]] + ； 1 HNMR(6、CDCl 3 )：8.77～8.76(4H，d)；8.35～8.31(2H，m)；8.24～8.20(2H，m)；8.05～8.03(1H，m)；7.92～7.85(5H，m)；7.53～7.41(8H，m)。
Referring to the above-described similar synthetic method, the following compounds shown in table 1 were prepared:
TABLE 1
Figure BDA0004086805320000172
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Figure BDA0004086805320000181
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Figure BDA0004086805320000191
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Figure BDA0004086805320000201
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Figure BDA0004086805320000211
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Figure BDA0004086805320000221
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Figure BDA0004086805320000231
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Figure BDA0004086805320000241
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Figure BDA0004086805320000251
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Figure BDA0004086805320000261
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Figure BDA0004086805320000271
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Figure BDA0004086805320000281
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Figure BDA0004086805320000291
Example 2
As shown in fig. 1, the OLED element of the present embodiment is a top emission light element, and includes a substrate 101, an anode layer 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode layer 102, a hole transport layer 104 disposed on the hole injection layer 103, an electron blocking layer 105 disposed on the hole transport layer 104, an organic light emitting layer 106 disposed on the electron blocking layer 105, a hole blocking layer 107 disposed on the organic light emitting layer 106, an electron transport layer 108 disposed on the hole blocking layer 107, an electron injection layer 109 disposed on the electron transport layer 108, and a cathode 110 disposed on the electron injection layer 109 and a capping layer 111 disposed on the cathode, wherein the method for preparing the OLED element excluding the hole blocking layer 107 includes the following steps:
1) The glass substrate coated with the ITO conductive layer is subjected to ultrasonic treatment in a cleaning agent for 30 minutes, rinsed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dried, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the above ITO glass substrate in vacuum chamber, and vacuumizing to less than 1×10 -5 Pa, depositing metallic silver as an anode layer on the ITO film, the thickness of the deposited film being
Figure BDA0004086805320000301
Continuing to vapor deposit the compounds HI01 and F4TCNQ respectively as hole injection layersWherein F4TCNQ is 3% of HI01 mass, and the vapor deposition film thickness is +.>
Figure BDA0004086805320000302
3) Continuously evaporating compound CPD as hole transport layer on the hole injection layer to obtain an evaporating film with a thickness of
Figure BDA0004086805320000303
4) Continuously evaporating compound EBL as electron blocking layer on the hole transport layer to obtain an evaporating film thickness of
Figure BDA0004086805320000304
5) Continuously evaporating compound RH11 as a main material and RD11 as a doping material on the electron blocking layer, wherein RD11 is 3% of the mass of the compound RH11, and the film thickness of the organic light-emitting layer obtained by evaporation is as the organic light-emitting layer of the element
Figure BDA0004086805320000305
6) Continuing to vapor deposit a layer of LiQ and the compound of formula (I) as an electron transport layer of the element on the organic light-emitting layer, wherein the compound of formula (I) is 50% of the mass of LiQ, and the vapor deposition film thickness is
Figure BDA0004086805320000306
7) Continuously evaporating a LiF layer on the electron transport layer to form an electron injection layer with an evaporating film thickness of
Figure BDA0004086805320000307
8) Evaporating metal magnesium and silver on the electron injection layer to serve as a transparent cathode layer of the element, wherein the mass ratio of the magnesium to the silver is 1:10, the thickness of the vapor deposition film is
Figure BDA0004086805320000308
9) Vapor-depositing CPD on the transparent cathode layer as elementCPL layer of (C), the vapor deposition film thickness is
Figure BDA0004086805320000309
To an OLED element provided by the present invention.
The structure of the compound used in example 2 above is as follows:
Figure BDA00040868053200003010
example 3
An organic electroluminescent device 200, the structure of which is shown in fig. 2, comprises a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first light emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213.
Comparative example 1
By following the same procedure as in example 2, substituting the compound of formula (I) in step 6) with E01, comparative element 1 is obtained;
Figure BDA0004086805320000311
comparative example 2
By following the same procedure as in example 2, substituting the compound of formula (I) in step 6) with E02, comparative element 2 is obtained;
Figure BDA0004086805320000312
comparative example 3
By following the same procedure as in example 2, the compound of formula (I) in step 6) is replaced by E03, giving comparative element 3;
Figure BDA0004086805320000313
Comparative example 4
By following the same procedure as in example 2, the compound of formula (I) in step 6) is replaced by E04, giving comparative element 4;
Figure BDA0004086805320000314
the organic electroluminescent element prepared by the above process was subjected to the following performance test:
the driving voltage and current efficiency and the lifetime of the elements of the organic electroluminescent elements prepared in examples 2 and 3 and comparative examples 1 to 4 were measured using a digital source meter and a luminance meter. Specifically, the luminance of the organic electroluminescent element was measured to reach 1000cd/m by increasing the voltage at a rate of 0.1V per second 2 The voltage at the time is the driving voltage, and the current density at the time is measured; the ratio of brightness to current density is the current efficiency; LT95% life test is as follows: at 1000cd/m using a luminance meter 2 The luminance decay of the organic electroluminescent element was measured to be 950cd/m while maintaining a constant current at luminance 2 Time in hours. The data listed in table 2 are the data in parentheses in comparative element 1 (test material E01) as compared to the relative data of comparative element 1.
TABLE 2
Figure BDA0004086805320000315
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Figure BDA0004086805320000321
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Figure BDA0004086805320000331
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Figure BDA0004086805320000341
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Figure BDA0004086805320000351
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Figure BDA0004086805320000361
As can be seen from Table 2, the device prepared from the heterocyclic compound of the present invention has a lower driving voltage than E01 under the same brightness, a significantly improved current efficiency up to as much as 1.2 times that of the comparative device, and a significantly improved LT95% lifetime of the device.
The compound E01 of comparative example 1 is different from the compound of the present invention in that the 2, 5-position of 1,3, 4-oxadiazole is an electron donating phenyl group, and an electron donating-electron withdrawing (D-a) type molecule is formed after the introduction of a triazine group having strong electron withdrawing, the electron cloud density of the 1,3, 4-oxadiazole group is reduced, the charge transport property is reduced, and the voltage is high and the efficiency is low. The compound of the invention enhances the electron withdrawing capability of the oxadiazole group to form electron withdrawing-electron withdrawing (A-A) molecules after introducing heteroaryl at the 2 position of 1,3, 4-oxadiazole, has more excellent performance in molecular film formation and charge transmission, and more balanced charge transmission in the element, so that the element performance is obviously improved.
The compound E02 of comparative example 2 is different from the compound of the present invention in that two triazine groups are simultaneously introduced on the 2, 5-phenyl groups of 1,3, 4-oxadiazole to form symmetrical molecules, and the electron cloud density of the oxadiazole group in the center of the molecule is reduced due to the strong electron withdrawing of the triazine groups, the charge transport performance is reduced, and the resulting voltage is high and stability is reduced. The compound of the invention adds electron-withdrawing heteroaryl at the 2-position of oxadiazole, the electron cloud distribution of molecules reaches balance, the performance of the compound is more excellent in molecular film formation and charge transmission, and the charge transmission in the element is more balanced, so the element performance is obviously improved.
The compound E03 of comparative example 3 is different from the compound of the present invention in that two 2-phenyl groups of 1,3, 4-oxadiazoles are linked to one triazine group, the highest occupied orbitals of the molecule are distributed on the two oxadiazole groups, and the planar conjugation ability of the oxadiazole groups is weak, and thus, the film-forming and charge-transporting properties of the molecule are degraded, resulting in reduced efficiency.
The compound E04 of comparative example 4 is different from the compound of the present invention in that the 2-position of 1,3, 4-oxadiazole is phenyl, and only after the substituted pyrimidinyl group is introduced at the 5-position, the planar conjugation ability is lowered, the molecular film forming and charge transporting properties are lowered, resulting in high voltage and reduced efficiency. The compound optimizes the molecular design, introduces electron-withdrawing groups at the 2-position of 1,3, 4-oxadiazole to form strong electron-withdrawing groups together, and introduces electron-withdrawing groups at the 5-position to form a-shaped molecule so as to improve the electron transmission performance, so that the compound has more excellent performance in molecular film formation and charge transmission, and more balanced charge transmission in the element, and the element performance is obviously improved.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (10)

1. A heterocyclic compound is characterized in that the structural formula is shown in a formula (I):
Figure FDA0004086805310000011
wherein,,
Ar 1 selected from the group consisting of substituted and unsubstituted C 2 -C 60 Heteroaryl groups;
L 1 selected from the group consisting of substituted and unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroarylenes;
L 2 、L 3 each independently selected from the group consisting of single bond, substituted or unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroarylenes;
X 1 、X 2 、X 3 each independently is CR 1 Or N, and X 1 、X 2 、X 3 Wherein the total number of N is 1 or 3; r is R 1 Selected from hydrogen, deuterium, fluorine, nitrile, nitro, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, substituted or unsubstituted C 1 -C 40 Alkyl, substituted or unsubstituted C 1 -C 40 Alkoxy, substituted or unsubstituted C 2 -C 40 Alkenyl, substituted or unsubstituted C 1 -C 40 Alkylthio, substituted or unsubstituted C 1 -C 40 Alkoxy, substituted or unsubstituted C 3 -C 40 Cycloalkyl, substituted or unsubstituted C 1 -C 40 Alkyl sulfoxide group, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 6 -C 60 Aryl sulfoxide group, substituted or unsubstituted C 3 -C 40 Silyl, substituted or unsubstituted boron, substituted or unsubstituted amine, substituted or unsubstituted aryl phosphine, substituted or unsubstituted phosphine oxide, or substituted or unsubstituted C 2 -C 60 Heteroaryl groups;
Ar 2 、Ar 3 each independently selected from the group consisting of substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 Heteroaryl groups.
2. The heterocyclic compound according to claim 1, wherein R 1 Selected from hydrogen, deuterium, fluorine, nitrile, methyl, phenyl, and biphenylA group consisting of terphenyl, naphthyl, pyridyl, phenanthryl, triphenylenyl, carbazolyl, fluorenyl, dibenzofuranyl, or dibenzothiophenyl;
Ar 2 、Ar 3 each independently selected from the group consisting of phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthryl, pyrenyl,
Figure FDA0004086805310000021
a group, perylene group, fluoranthenyl group, naphthacene group, pentacene group, benzopyrene group, biphenyl group, terphenyl group, tripolyphenyl group, tetrabiphenyl group, fluorenyl group, spirobifluorenyl group, dihydrophenanthrene group, triphenylene group, dihydropyrenyl group, tetrahydropyrenyl group, cis-or trans-indenofluorenyl group, cis-or trans-indenocarbazolyl group, indolocarbazolyl group, benzofuranocarbazolyl group, benzothiophenocarbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, azadibenzo [ g, ij]Naphtho [2,1,8-cde ]Azulene, triindenyl, heterotrimeric indenyl, spirotrimeric indenyl, spiroheterotrimeric indenyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, pyridyl, quinolinyl, isoquinolinyl, acridinyl, phenanthridinyl, benzo [5,6 ]]Quinolinyl, benzo [6,7]Quinolinyl, benzo [7,8]Quinolinyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthaminyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthazolyl, anthracnose oxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthryl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazaanthracenyl, 2, 7-diazapyrenyl, 2, 3-diazapyrenyl, 1, 6-diazapyrenyl, 1, 8-diazapyrenyl, 4,5,9, 10-tetraazaperylene, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorozinyl, naphthyridinyl, azacarbazolyl, benzocarboline, carboline, phenanthroline, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazole, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, quinazolinyl, benzothiadiazolyl, or groups derived from combinations of these systems.
3. The heterocyclic compound according to claim 1, wherein Ar 1 Selected from the group consisting of the groups shown in II-1 to II-13 below:
Figure FDA0004086805310000031
wherein,,
Z 1 、Z 2 each independently selected from the group consisting of hydrogen, deuterium, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 40 Alkyl, C 2 -C 40 Alkenyl, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy, C 3 -C 40 Naphthene radical, C 3 -C 40 Cycloalkenyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Aryl sulfide group, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 Heteroaryl groups;
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
T 1 representation O, S or NAr’；
Ar' is selected from C 1 ～C 40 Alkyl, C of (2) 1 ～C 40 Heteroalkyl of (C) 3 ～C 40 Cycloalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 Heteroaryl groups; preferably, ar' is methyl, ethyl, phenyl, biphenyl or naphthyl;
Figure FDA0004086805310000042
ar is represented by 1 A linkage to 1,3, 4-oxadiazole.
4. The heterocyclic compound according to claim 1, wherein L 1 Selected from the group consisting of groups represented by III-1 to III-25; l (L) 2 、L 3 Each independently selected from the group consisting of single bonds or groups represented by III-1 to III-25:
Figure FDA0004086805310000041
wherein X is selected from O, S, se, CR 2 R 3 、SiR 2 R 3 Or NAr 3 ；
Z 11 、Z 12 、Z 13 、Z 14 Each independently selected from the group consisting of hydrogen, deuterium, halogen atoms, hydroxyl, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 60 Alkyl, C of (2) 2 -C 60 Alkenyl, C 2 -C 60 Alkynyl, C 1 -C 60 Alkoxy, C 3 -C 60 Is C 3 -C 60 Cyclic olefin group, substituted or unsubstituted C 6 -C 60 Aryl, takeSubstituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Aryl sulfide group, or substituted or unsubstituted C 2 -C 60 Heteroaryl groups;
y1 represents an integer of 1 to 4; y2 represents an integer of 1 to 6; y3 represents an integer of 1 to 3; y4 represents an integer of 1 to 5; y5 represents an integer of 1 or 2;
R 2 、R 3 each independently selected from the group consisting of C 1 -C 60 Alkyl, C of (2) 1 -C 60 Is optionally substituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 Heteroaryl group, R 2 And R is 3 Optionally joined or fused to form one or more additional substituted or unsubstituted rings with or without one or more heteroatoms N, P, B, O or S in the formed ring; preferably, R 2 、R 3 Methyl, phenyl or fluorenyl;
Ar 3 selected from C 1 -C 60 Alkyl, C of (2) 1 -C 60 Heteroalkyl of (C) 3 -C 60 Cycloalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 Heteroaryl groups; preferably Ar 3 Methyl, ethyl, phenyl, biphenyl or naphthyl;
Wherein the dotted line represents the attachment site of the group.
5. The heterocyclic compound according to claim 1, wherein the heterocyclic compound is selected from the group consisting of compounds represented by the following formulas J475-J663:
Figure FDA0004086805310000051
/>
Figure FDA0004086805310000061
/>
Figure FDA0004086805310000071
/>
Figure FDA0004086805310000081
/>
Figure FDA0004086805310000091
/>
Figure FDA0004086805310000101
/>
Figure FDA0004086805310000111
/>
Figure FDA0004086805310000121
/>
Figure FDA0004086805310000131
/>
Figure FDA0004086805310000141
6. use of the heterocyclic compound according to any one of claims 1 to 5 for producing an organic electroluminescent element.
7. An organic electroluminescent element, characterized in that it comprises: a first electrode, a second electrode, a capping layer, and one or more organic layers disposed between the first electrode and the second electrode; a material of at least one of the organic layer or the capping layer comprises the heterocyclic compound according to any one of claims 1 to 5.
8. The organic electroluminescent element according to claim 7, wherein the organic layer comprises a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, or an electron blocking layer.
9. The organic electroluminescent element according to claim 8, wherein the light-emitting layer, the electron-transporting layer, the electron-injecting layer, or the hole-blocking layer contains the heterocyclic compound according to any one of claims 1 to 5.
10. A consumer product comprising the organic electroluminescent element of claim 7.
CN202310138519.5A 2023-02-15 2023-02-15 Heterocyclic compound and application thereof Pending CN116023374A (en)

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