CN117756830A - Heterocyclic compound containing boron atom and application thereof - Google Patents

Heterocyclic compound containing boron atom and application thereof Download PDF

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Publication number
CN117756830A
CN117756830A CN202311691111.7A CN202311691111A CN117756830A CN 117756830 A CN117756830 A CN 117756830A CN 202311691111 A CN202311691111 A CN 202311691111A CN 117756830 A CN117756830 A CN 117756830A
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substituted
unsubstituted
group
aryl
heterocyclic compound
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曹建华
郭晓慧
张宇炜
唐怡杰
张昊
边坤
刘晨曦
洪丽
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Zhejiang Bayi Space Time Advanced Materials Co ltd
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Zhejiang Bayi Space Time Advanced Materials Co ltd
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Abstract

The invention relates to the technical field of organic electroluminescent materials, in particular to a heterocyclic compound containing boron atoms and application thereof. The structural formula of the heterocyclic compound containing boron atoms is shown as a formula (I); the invention provides a compound shown in formula (I) with boron-containing sourceHeterocyclic structure of the child. 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;

Description

Heterocyclic compound containing boron atom and application thereof
cross reference
The present application claims priority from chinese patent application CN202311232523.4 on application date 2023, 09, 22. The present application refers to the entirety of the above-mentioned chinese patent application.
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 recent years, organic electroluminescent display technology has tended to mature, some products have been brought into the market, but in the industrialization process, there are still many problems to be solved, especially, various organic materials for manufacturing elements, such as carrier injection and transmission performance, electroluminescent performance, service life, color purity, matching between various materials and various electrodes, and the like, have not been solved. In particular, the light-emitting element has not yet reached practical requirements in terms of light-emitting efficiency and service life, which greatly limits the development of OLED technology.
Organic electroluminescence is largely classified into fluorescence and phosphorescence, but according to spin quantum statistics theory, the probability of singlet excitons and triplet excitons is 1:3, i.e., the theoretical limit of fluorescence from singlet exciton radiative transitions is 25% and the theoretical limit of fluorescence from triplet exciton radiative transitions is 75%. How to use the energy of 75% of triplet excitons becomes urgent. The fact that the phosphorescence electroluminescence phenomenon breaks through the limit of 25% efficiency of the quantum efficiency of the organic electroluminescence material in 1997 is found by Forrest and the like, and the wide attention of people on the metal complex phosphorescence material is brought. Since then, a great deal of research has been conducted on phosphorescent materials.
The present invention has been made in view of the above-mentioned circumstances.
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):
Wherein A represents a group represented by formula (II);
R 1 、R 2 、R 3 each represents one or more to saturated substituents, identically or differently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile groups, 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 sulfonyl, 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 sulfonyl, 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 A heterocyclic aryl group, and R 1 、R 2 、R 3 And L 1 Connecting; any two or more substituents adjacent to each other may be optionally joined or fused to form a substituted or unsubstituted ring;
x is selected from O, S, SO, SO 2 、C＝O、Se、CR 4 R 5 、SiR 4 R 5 Or NAr 3 ；
L 1 Selected from single bonds, substituted or unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroarylenes;
Z 1 、Z 2 、Z 3 Each independently represents CR 6 Or N;
R 4 、R 5 、R 6 each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, 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 sulfonyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstitutedSubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 6 -C 60 Aryl sulfonyl, 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 A group consisting of heteroaryl groups; any two or more substituents adjacent to each other may be optionally joined or fused to form a substituted or unsubstituted ring;
Ar 1 、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 Arylamine groups, or substituted or unsubstituted C 2 -C 60 A heterocyclic aryl group.
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 A containing a boron atom as the center is represented by L of a single bond, arylene, heteroarylene 1 And is combined with pyridine, pyrimidine, triazine, or the like to form a basic skeleton. The compound represented by the formula (I) of the present invention is not only electrochemically stable, but also excellent in electron mobility, and has a high glass transition temperature and excellent thermal stability, as compared with conventionally known heterocyclic structures having a boron atom as the center. 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 hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a hole blocking layer of an organic electroluminescent element. Preferably usable as any one of a light-emitting layer, an electron transport layer, and an electron transport auxiliary layer laminated in one step on the electron transport layer,more preferably, a material which can be used as a light-emitting layer or an electron transport layer.
Specifically, the compound represented by the formula (I) of the present invention has a higher electron-transporting ability than a heterocycle such as dibenzofuran or dibenzothiophene having a lower electron-withdrawing group ability by containing a boron atom-centered heterocyclic compound and a group such as pyrimidine or triazine having a higher electron-withdrawing ability, 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 can the thermal stability, carrier transporting ability, electron transporting ability and light emitting ability be excellent, but also the driving voltage of the element can be reduced, the efficiency and lifetime can be improved, and as a material for a latest electron transporting layer, an excellent efficiency increase due to a triplet-triplet amyl fusion effect can be exhibited due to a high triplet energy level.
In addition, the heterocyclic compound of formula (I) of the present invention is obtained by introducing a plurality of substituents R into the basic skeleton 1 、R 2 、R 3 、Ar 3 And the like, and the HOMO and LUMO energy levels are adjusted according to the kind of the substituent, so that the organic electroluminescent element using such a compound can have a wide band gap, and the electron transport property can be remarkably improved.
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 、Ar 1 、Ar 2 The molecular weight of the compound is significantly increased by the iso-groups, especially aryl and/or heteroaryl, and the glass transition temperature is increased, so that the compound has higher thermal stability than the prior luminescent materials, such as phenanthridine. 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.
The heterocyclic compound represented by the formula (I) of the present invention is preferably selected from the group consisting of:
wherein the symbols used have the same meanings as defined above.
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.
Further, the aryl, heteroaryl or heteroaryl group is preferably selected from the group consisting of phenyl, naphthyl, anthryl, benzanthraceyl, phenanthryl, pyrenyl,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]Azulenyl, trimeric indenyl, heterotrimeric indenyl, spirotrimeric indenyl, spiroheterotrimeric indenyl, furyl, benzofuryl, isobenzofurolPyranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, 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, naphthamidinyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthazolyl, anthracoxazolyl, 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, fluororubenyl, 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, naphthyridinyl, quinazolinyl, and benzothiadiazolyl or combinations thereof.
Further, the R 1 、R 2 、R 3 Each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile groups, substituted or unsubstituted phenyl groups, substituted or unsubstituted carbazolyl groups;
further, the Ar 1 、Ar 2 、Ar 3 Each independently selected from the group consisting of substituted or unsubstituted: phenyl, naphthyl, anthryl, benzanthraceyl, phenanthryl, pyrenyl,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]Azulenyl, trimeric indenyl, 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, naphthamidinyl, 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-diazapyrenyl, 4,5,9, 10-tetraazaperylene group, pyrazinyl group, phenazinyl group, phenoxazinyl group, phenothiazinyl group, fluorogenic ring 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 group, 1,2, 5-thiadiazolyl group, 1,3, 5-triazinyl group, 1,2, 4-triazinyl group, 1,2, 3-triazinyl group, tetrazolyl group, 1,2,4, 5-tetrazinyl group, 1,2,3, 4-tetrazinyl group, 1,2, 3-tetrazinyl group, 1, 3-tetrazolyl group, 3-thiazinyl group, 1, 4-thiazolyl group, quinazolinyl group, and pteridine group Diazolyl or a group derived from a combination of these systems.
Further, the X is selected from O, S, se, CR 4 R 5 Or NAr 3 。
Further, the R 4 、R 5 、R 6 Each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, methyl, ethyl, substituted or unsubstituted phenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl.
Further, the heteroaryl or heteroaryl group is selected from the group consisting of the groups shown in II-1 to II-17 below:
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, or substituted or unsubstituted C 5 ～C 60 A group consisting of 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, CR ’ R' or NAr ’ ；
R ’ R' are each independently selected from hydrogen, deuterium, C 1 ～C 40 Alkyl, C of (2) 1 ～C 40 Is substituted by heteroalkyl groups of (2)Or unsubstituted C 6 ～C 60 Aryl, substituted or unsubstituted C 6 ～C 60 Arylamine groups, or substituted or unsubstituted C 5 ～C 60 A group consisting of heterocyclic aryl groups, R ’ And R "may optionally be 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 ring formed; preferably, R ’ R' is methyl, phenyl or fluorenyl;
Ar ’ 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 10 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 ～C 60 Arylamine groups, or substituted or unsubstituted C 5 ～C 60 A group consisting of heteroaryl groups; preferably Ar ’ Methyl, ethyl, phenyl, biphenyl or naphthyl;
indicating the location of the bond.
In the heterocyclic compound of formula (I) of the present invention, L 1 The functional group for connecting the boron atom-centered heterocyclic skeleton A to the electron-withdrawing group may be selected from the group consisting of a single bond and C 6 -C 60 Arylene and C of (2) 2 -C 60 A group of heteroarylenes. In this case, preferably, the L 1 Selected from a single bond or one of substituted or unsubstituted formulas (20) to (35), the specific structural formulas of formulas (20) to (35) are as follows:
Wherein Y is selected from O, S, SO, SO 2 、Se、CR ’ R”、SiR ’ R' or NAr ’ ；
R meterOne, two or more to saturation substitution; 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;
R ’ r' are each independently selected from 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 ’ And R "may optionally be 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 ring formed; preferably, R ’ R' is hydrogen, methyl, phenyl or fluorenyl;
Ar ’ 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 10 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups; preferably Ar ’ Methyl, ethyl, phenyl, biphenyl or naphthyl;
wherein the dotted line represents the attachment site of the group, and in this case, the binding sites of the groups represented by the above formulas (20) to (35)The arrangement is not limited, and can be adjacent, inter and opposite. L as described above 1 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.
"halogen", "halogen atom", "halo" in the sense of the present invention are used interchangeably and refer to fluorine, chlorine, bromine or iodine.
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, pentynylHexynyl, 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 with oxygen, sulfur, halogen atoms, as non-limiting examples, alkoxy, alkylthio, fluoroalkoxy, fluoroalkylthio, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, trifluoromethylthio, trifluoromethoxy, pentafluoroethoxy, pentafluoroethylthio, 2-trifluoroethoxy, 2-trifluoroethylthio, ethyleneoxy, ethylenethio, propyleneoxy, propylenethio, butylenethio, butyleneoxy, pentenyloxy, pentenylthio, cyclopentenyloxy, cyclopentenylthio, hexenyloxy, hexenylthio, cyclohexene thio, acetylenyloxy, acetylenylthio, propynyloxy, butynylthio, pentynyloxy, pentynylthio, hexyloxy, hexylynylthio.
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, there are tetrahydrofuranyl, tetrahydrothienyl, morpholinyl, piperazinyl, 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,A base, etc.
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 in the present invention means R b O - A monovalent functional group represented by R b Is an alkyl group having 1 to 40 carbon atoms, and may contain a linear, branched 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.
Aryloxy as used herein refers to R c O - Represented monovalent functional groups, R is the above c 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 arylphosphino group used in the present invention means a diarylphosphino group substituted with an aryl group having 6 to 60 carbon atoms, and as non-limiting examples of the arylphosphino group, there are diphenylphosphino group, bis (4-trimethylsilylbenzene) phosphino group and the like. The phosphorus atom of the arylphosphinyl group, which is a diarylphosphinyl 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.
"sulfoxide" in the sense of the present invention means-SOR a A group.
"sulfone" in the sense of the present invention means-SO 2 R a A group.
"phosphino" in the sense of the present invention means-PO (R a ) 3 A group wherein each R a May be the same or different.
Each R as described above a Preferably selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl as defined above.
Preferably, the heterocyclic compound is selected from compounds represented by the following formulas E200-E403:
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wherein T is selected from O, S, se, CMe 2 、CPh 2 、NPh、NPhPh；
X is selected from O, S, CMe 2 NPh or NPhPh;
me represents methyl, ph represents phenyl, phPhPh represents biphenyl;
some or all of the hydrogen atoms in the above structures may be replaced with deuterium atoms.
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。
Organic electroluminescent elements which are produced by means of organic vapor deposition methods or by means of organic vapor deposition methods are likewise preferred Applying one or more layers by sublimation in a carrier gas, wherein 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 at least one layer being applied by means of an organic vapour deposition method or by means of carrier gas sublimation and/or at least one layer being 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.
Preferably, the light-emitting layer, electron-transporting layer or hole-blocking layer comprises the heterocyclic compound of the present invention.
The light emitting layer may include a host material including a fused aromatic ring derivative or a compound containing a heterocycle, and a dopant material. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and the heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, pyrimidine derivatives, and the like, but are not limited thereto.
Preferably, the light emitting layer may include a heterocyclic compound represented by formula (I) as a host material, and at the same time, the light emitting layer may further include a compound represented by formula (III):
in the formula (III), ar 4 、Ar 5 Each independently selected from the group consisting of substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 10 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups;
R represents 1, 2 or more to saturated substitution, and the meaning of R is the same as defined above.
Preferably, the compound represented by the formula (III) may be contained as a host material in the light emitting layer together with the heterocyclic compound represented by the formula (I).
Preferably, the Ar 4 、Ar 5 Each independently selected from the group consisting of substituted or unsubstituted C 6 -C 60 Aryl, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups;
more preferably, the Ar 4 、Ar 5 Each independently selected from a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, or a substituted or unsubstituted fluorenyl group.
Preferably, each R is independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, substituted or unsubstituted C 6 -C 60 Aryl, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups;
more preferably, each R is independently selected from hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl.
Further, representative examples of the compound represented by the formula (III) are as follows:
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wherein Y is selected from O, S or CMe 2 ；
Some or all of the hydrogen atoms in the above structures may be replaced with deuterium atoms.
The doping material includes aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the arylamine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamine group, such as pyrene, anthracene, chrysene, violanthrene, etc. having an arylamine group, and the styrylamine compound includes a substituted or unsubstituted arylamine group substituted with at least one arylvinyl group in which one or two or more substituents selected from the group consisting of aryl, silyl, alkyl, cycloalkyl, and arylamine groups are substituted or unsubstituted, and specifically includes, but is not limited to, styrylamine, styrylenediamine, styryltriamine, styrenetetramine, etc. In addition, the metal complexes include, but are not limited to, iridium complexes and platinum complexes.
The invention also provides a consumer product comprising the organic electroluminescent element. The consumer product described in the present invention may be one of the following devices: flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cellular telephones, tablet computers, tablet handsets, personal Digital Assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, micro-displays with a diagonal of less than 2 inches, 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising a plurality of displays tiled together, theatre or gym screens, phototherapy devices, and billboards.
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, an electron transport auxiliary layer, or a light-emitting 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, an organic 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 comprises 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 the 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: photoresearch PR-715 was tested using a spectrum scanner;
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 E240, exemplified by x=o, comprising the steps of:
the first step: preparation of intermediate Int-1
Under the protection of nitrogen, 20.0mmol of sub-1 and 24.0mmol of sub-2 are dissolved in 60mL of toluene, and then 60.0mmol of hydrated potassium phosphate and 0.1mmol of Pd (PPh) are added 3 ) 4 Heating to reflux with 30mL of water and 30mL of ethanol, stirring for reaction for 10 hours, cooling to room temperature, adding 50mL of water, separating an organic phase, extracting the aqueous phase with ethyl acetate, combining the organic phases, drying, filtering, concentrating and drying the filtrate under reduced pressure, and separating and purifying by a silica gel column to obtain a compound Int-1 as a white solid with the yield: 82%.
And a second step of: preparation of intermediate Int-2
Under the protection of nitrogen, 20.0mmol of Int-1 prepared in the previous step is dissolved in 60mL of dry dimethylbenzene, the temperature is reduced to minus 78 ℃,24.0mmol of 2.5M n-butyllithium n-hexane solution is added dropwise, stirring reaction is carried out for 10 minutes, 25.0mmol of boron tribromide is added dropwise, the temperature is slowly raised to room temperature, stirring reaction is carried out for 1 hour, 0.1mol of diisopropylethylamine is added, heating is carried out to reflux, stirring reaction is carried out for 15 hours, cooling is carried out to room temperature, filtration is carried out, a filter cake is washed by dichloromethane, filtrate is concentrated to dryness under reduced pressure, and the compound Int-2 is obtained by separating and purifying by a silica gel column, and is a white solid with the yield of 57%.
And a third step of: preparation of intermediate Int-3
Under the protection of nitrogen, 24.0mmol of sub-3 and 20.0mmol of sub-4 are dissolved in 60mL of toluene, 60.0mmol of anhydrous potassium carbonate, 0.01mmol of Pd132, 30mL of water and 30mL of ethanol are added, the mixture is heated to reflux, the mixture is stirred for reaction for 10 hours, cooled to room temperature, 50mL of water is added, an organic phase is separated, the aqueous phase is extracted by ethyl acetate, the organic phases are combined, dried, filtered, the filtrate is concentrated and dried under reduced pressure, and the compound Int-3 is obtained by separating and purifying by a silica gel column, and the yield is obtained: 74%.
Fourth step: preparation of intermediate Int-4
Under the protection of nitrogen, 20.0mmol of Int-3 prepared in the previous step is dissolved in 60mL of DMF, and 24.0mmol of pinacol biborate, 30.0mmol of anhydrous potassium acetate, 2.0mmol of cuprous iodide and 0.2mmol of catalyst PdCl are added 2 (dppf)CH 2 Cl 2 Heating to 100 ℃, stirring and reacting for 15 hours, cooling to room temperature, adding 150mL of ice water, extracting with ethyl acetate, washing an organic phase with saturated brine, drying, filtering, concentrating and drying filtrate under reduced pressure, and separating and purifying with a silica gel column to obtain a compound Int-4, white solid, and the yield is 86%.
Fifth step: preparation of Compound E240
24.0mmol of Int-4 prepared in the previous step, 20.0mmol of Int-2 and 60mL of toluene are mixed under the protection of nitrogen, 60.0mmol of anhydrous potassium carbonate, 0.01mmol of Pd132 catalyst, 30mL of water and 30mL of ethanol are added, the mixture is heated, refluxed and stirred for reaction for 15 hours, 50mL of water is added, the organic phase is separated, the aqueous phase is extracted by methylene dichloride, the organic phases are combined, dried, filtered, the filtrate is concentrated and dried under reduced pressure, separated and purified by a silica gel column, and then the mixture is recrystallized by methylene dichloride/ethanol to obtain a compound E240 (X=O), a white solid with the yield of 75 percent, MS (TOF) m/z:702.2293[ M+H ]]； 1 HNMR(δ、CDCl 3 )：8.84(1H,s)；8.38～8.34(4H,m)；8.19(1H,s)；8.02～7.99(1H,d)；7.88～7.79(4H,m)；7.72～7.63(5H,m)；7.58～7.50(6H,m)；7.45～7.41(3H,m)；7.34～7.30(1H,m)；7.13～7.08(2H,m)。
Referring to the above-described similar synthetic method for preparing a compound of x=s, only the first step of sub-2 was replaced with (4-chloro-3- (phenylsulfanyl) phenyl) boronic acid, a white solid, yield 74%, MS (TOF) m/z:718.2064[ M+H ] ]； 1 HNMR(δ、CDCl 3 )：8.84(1H,s)；8.38～8.34(4H,m)；8.19(1H,s)；8.11～8.09(1H,m)；7.89～7.80(4H,m)；7.78～7.65(5H,m)；7.58～7.50(6H,m)；7.45～7.41(3H,m)；7.38～7.35(1H,m)；7.18～7.14(1H,m)；7.11～7.08(1H,m)。
Example 2
A process for the preparation of compound E396, exemplified by x=o, comprising the steps of:
the first step: preparation of intermediate Int-5
Under the protection of nitrogen, 20.0mmol of Int-2' (prepared by the synthetic method of example 1), 24.0mmol of sub-5 are dissolved in 60mL of toluene, 60.0mmol of anhydrous potassium carbonate, 0.01mmol of Pd132 and 30mL of water are added, the mixture is heated to reflux, stirred and reacted for 15 hours, cooled to room temperature, 50mL of water is added, an organic phase is separated, the aqueous phase is extracted by ethyl acetate, the organic phases are combined, dried, filtered, the filtrate is concentrated and dried under reduced pressure, and the compound Int-5 is obtained by separating and purifying by a silica gel column, yellow solid is obtained, and the yield: 73%.
And a second step of: preparation of Compound E396
Under the protection of nitrogen, 20.0mmol of Int-5 prepared in the previous step is dissolved in 50mL of DMF, the temperature is reduced to 0 ℃, 24.0mmol of 60% sodium hydride oil is added in portions to disperse solid, stirring reaction is carried out for 1 hour, 24.0mmol of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine is added, the temperature is raised to room temperature, stirring reaction is carried out for 12 hours, reaction liquid is poured into 150mL of ice water, filtration is carried out, filter cakes are washed with water and ethanol, solid is separated and purified by a silica gel column, and then THF/ethanol is used for recrystallization, thus obtaining compound E396 (X=O), yellow solid with the yield of 87 percent, MS (TOF) m/z:701.2526[ M+H ] ]； 1 HNMR(δ、CDCl 3 )：8.94(1H,s)；8.59～8.55(4H,m)；8.32(1H,s)；8.21～8.13(4H,m)；7.92～7.79(6H,m)；7.55～7.51(2H,m)；7.48～7.39(8H,m)；7.36～7.34(1H,m)；7.23～7.19(1H,m)；7.11～7.07(1H,m)。
The compound of x=s was prepared with reference to the similar synthetic method described above, as a yellow solid in 87% yield, MS (TOF) m/z:717.2224[ M+H ]]； 1 HNMR(δ、CDCl 3 )：8.95(1H,s)；8.59～8.53(5H,m)；8.46～8.44(1H,m)；8.15～8.09(3H,m)；7.99～7.97(1H,d)；7.92～7.90(1H,m)；7.82～7.75(3H,m)；7.72～7.68(2H,m)；7.56～7.51(2H,m)；7.45～7.36(8H,m)；7.29～7.25(1H,m)；7.19～7.16(1H,m)。
Examples 3 to 93
Referring to the above-described similar synthetic method, the following compounds shown in table 1 were prepared:
TABLE 1
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In the above embodiments, X is O or S; t is selected from O, S, CMe 2 、CPh 2 、NPh、NPhPh；
Me is methyl, ph is phenyl, and PhPh is biphenyl.
Example 205
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 beingContinuing to vapor deposit the compounds HI01 and F4TCNQ as hole injection layers respectively, wherein F4TCNQ is 3% of HI01 by mass, and the vapor deposition film thickness is +.>
3) Continuously evaporating compound HTM as hole transport layer on the hole injection layer to obtain an evaporating film with a thickness of
4) Continuously evaporating compound EBL as electron blocking layer on the hole transport layer to obtain an evaporating film thickness of
5) The boron atom-containing heterocyclic compound and the compound GP7 shown in the formula (I) are continuously evaporated on the electron blocking layer to serve as main materials, and GD015 is used as a doping material, wherein the mass ratio of the GP7 to the compound shown in the formula (I) is 60:40, the GD015 is 6% of the mass of the main materials, the organic light-emitting layer is used as an element, and the film thickness of the organic light-emitting layer obtained by evaporation is
6) Continuously evaporating a LiQ and ET011 as electron transport layers of the element on the organic light-emitting layer, wherein the ET011 is 50% of the LiQ in mass, and the evaporating film thickness is
7) Continuously evaporating a LiF layer on the electron transport layer to form an electron injection layer with an evaporating film thickness of
8) Evaporating metal magnesium and silver on the electron injection layer to form a transparent cathode layer of the element, wherein the mass ratio of magnesium to silver is 1:9, and the film thickness of the evaporated film is
9) Evaporating CPD layer as CPL layer of the device on the transparent cathode layer to obtain an evaporated film thickness ofThe OLED element provided by the invention is obtained.
The structure of the compound used in example 205 above was as follows:
example 206
An organic electroluminescent device 200, as 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
According to the same procedure as in example 205, the boron atom-containing heterocyclic compound represented by the formula (I) of the present invention in step 5) was replaced with H01 and GP7, wherein the mass ratio of GP7 to H01 was 60:40, to obtain comparative element 1;
comparative example 2
According to the same procedure as in example 205, the boron atom-containing heterocyclic compound represented by the formula (I) of the present invention in step 5) was replaced with H02 and GP7, wherein the mass ratio of GP7 to H02 was 60:40, to obtain comparative element 2;
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 205, 206, comparative example 1 and comparative example 2 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 electricityFlow efficiency; LT95% life test is as follows: using a luminance meter at 10000cd/m 2 The luminance decay of the organic electroluminescent element was measured to be 9500cd/m while maintaining a constant current at luminance 2 Time in hours.
TABLE 2
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As is clear from Table 2, the element prepared from the heterocyclic compound of the present invention has a lower driving voltage than H01 and H02 under the same luminance, the current efficiency is remarkably improved, and the light-emitting element has a luminance of 10000cd/m 2 The LT95% life under the initial condition is greatly improved, which shows that the heterocyclic compound is a luminescent layer material with excellent performance.
The compound H01 of comparative example 1 is different from the compound of the present invention in that the planar conjugation of the boron heterocyclic group of H01 is small, exciton transport performance is weak, and the driving voltage is high and the efficiency is low. The heterocyclic compound of the invention uses naphthalene as boron heterocyclic group plane conjugation enhancement, and has more excellent performance in molecular film formation and exciton transmission, so that the transmission of charges in the element is more balanced, and the element performance is obviously improved.
The compound H02 of comparative example 2 is different from the compound of the present invention in that H02 is a TADF fluorescent molecule resonating at boron-oxygen, and hole transporting property is stronger than electron transporting property, and thus H02 and GP7 are p-type (hole type), resulting in imbalance in transportation of excitons in the element. The heterocyclic compound of the invention introduces electron-withdrawing groups such as pyridine, pyrimidine, triazine and other derivatives on the basis of the heterocyclic ring which uses boron-oxygen and boron-sulfur as resonance to form p-n bipolar molecules, so that after the heterocyclic compound is co-evaporated with p-type molecules of GP7 to form a film, the transfer of excitons is more balanced, and the element performance is obviously improved.
The above examples are given as representative examples only of the mass ratio of the compound GP7 and the heterocyclic compound 60:40 represented by formula (I) as host materials, and are not intended to be limiting. The mass ratio of the two compounds may be 99:1 to 1:99 as a host material, for example, the compound GP7 and the heterocyclic compound represented by formula (I) may be 50:50 mass ratio, or 55:45 mass ratio as a host material, and at the same time GP7 may be replaced by any one of GP1 to GP6 or GP8 to GP48, without affecting the conclusion of the above-described embodiments.
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):
wherein A represents a group represented by formula (II);
R 1 、R 2 、R 3 each represents one or more to saturated substituents, identically or differently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile groups, 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 sulfonyl, 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 sulfonyl, 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 A heterocyclic aryl group, and R 1 、R 2 、R 3 And L 1 Connecting; any two or more substituents adjacent to each other may be optionally joined or fused to form a substituted or unsubstituted ring;
x is selected from O, S, SO, SO 2 、C＝O、Se、CR 4 R 5 、SiR 4 R 5 Or NAr 3 ；
L 1 Selected from single bonds, substituted or unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroarylenes;
Z 1 、Z 2 、Z 3 each independently represents CR 6 Or N;
R 4 、R 5 、R 6 each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, 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 sulfonyl, 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 sulfonyl, 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 A group consisting of heteroaryl groups; any two or more substituents adjacent to each other may be optionally joined or fused to form a substituted or unsubstituted ring;
Ar 1 、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 Arylamine groups, or substituted or unsubstituted C 2 -C 60 A heterocyclic aryl group.
2. The heterocyclic compound of claim 1, wherein the heterocyclic compound is selected from the group consisting of:
wherein Z is 1 ～Z 3 、Ar 1 、Ar 2 、L 1 、R 1 ～R 3 And X has the same meaning as defined in claim 1.
3. The heterocyclic compound according to claim 1 or 2, wherein R 1 、R 2 、R 3 Each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile groups, substituted or unsubstituted phenyl groups, substituted or unsubstituted carbazolyl groups;
Ar 1 、Ar 2 、Ar 3 each independently selected from the group consisting of substituted or unsubstituted: phenyl, naphthyl, anthryl, benzanthraceyl, phenanthryl, pyrenyl,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]Azulenyl, trimeric indenyl, 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, naphthamidazolyl, phenanthroimidazolyl, pyridoimidazolyl pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl naphthooxazolyl, anthracooxazolyl, phenanthrooxazolyl, isoxazole1, 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, fluoroyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, carbolinyl, 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.
4. The heterocyclic compound according to claim 1, wherein X is selected from O, S, se, CR 4 R 5 Or NAr 3 ；
R 4 、R 5 、R 6 Each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, methyl, ethyl, substituted or unsubstituted phenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl.
5. The heterocyclic compound according to claim 1, wherein L 1 Selected from a single bond or one of substituted or unsubstituted formulas (20) to (35), the specific structural formulas of formulas (20) to (35) are as follows:
wherein Y is selected from O, S, SO, SO 2 、Se、CR ’ R”、SiR ’ R' or NAr ’ ；
R represents one, two or more to saturated substitution; 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;
R ’ r' are each independently selected from 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 ’ And R "may optionally be 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 ring formed; preferably, R', R "is hydrogen, methyl, phenyl or fluorenyl;
ar' is 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 10 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups; preferably, ar' is methyl, ethyl, phenyl, biphenyl or naphthyl;
the dotted line represents the attachment site of the group.
6. The heterocyclic compound according to any one of claims 1 to 5, wherein the heterocyclic compound is selected from compounds represented by the following formulae E200 to E403:
/>
wherein T is selected from O, S, se, CMe 2 、CPh 2 、NPh、NPhPh；
X is selected from O, S, CMe 2 NPh or NPhPh;
me represents methyl, ph represents phenyl, phPhPh represents biphenyl;
some or all of the hydrogen atoms in the above structures may be replaced with deuterium atoms.
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 includes the heterocyclic compound according to any one of claims 1 to 6.
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; the light-emitting layer, electron transporting layer, or hole blocking layer comprising the heterocyclic compound according to any one of claims 1 to 6.
9. The organic electroluminescent element according to claim 7 or 8, wherein the light-emitting layer comprises a host material and a doping material;
the host material comprising the heterocyclic compound according to any one of claims 1 to 6;
the host material may further include a compound represented by the following formula (III):
in the formula (III), ar 4 、Ar 5 Each independently selected from the group consisting of substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 10 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups;
r represents 1, 2 or moreTo saturation substitution, and R is each independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitrile group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a carboxylate thereof, a sulfonic acid group or a sulfonate thereof, a phosphoric acid group or a phosphate thereof, and C 1 -C 40 Alkyl, C of (2) 2 -C 40 Alkenyl, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy, C 3 -C 40 Is C 3 -C 40 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.
10. The organic electroluminescent element according to claim 9, wherein the Ar 4 、Ar 5 Each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, or substituted or unsubstituted fluorenyl;
each R is independently selected from hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl;
Preferably, the compound represented by the formula (III) is selected from the compounds represented by the following GP1 to GP 48:
/>
wherein Y is selected from O, S or CMe 2 ；
Some or all of the hydrogen atoms in the above structures may be replaced with deuterium atoms.
CN202311691111.7A 2023-09-22 2023-12-11 Heterocyclic compound containing boron atom and application thereof Pending CN117756830A (en)

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