CN115724826A - Heterocyclic compound and application thereof - Google Patents

Heterocyclic compound and application thereof Download PDF

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CN115724826A
CN115724826A CN202211328091.2A CN202211328091A CN115724826A CN 115724826 A CN115724826 A CN 115724826A CN 202211328091 A CN202211328091 A CN 202211328091A CN 115724826 A CN115724826 A CN 115724826A
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曹建华
姜卫东
王振宇
唐伟
刘赛赛
徐先锋
李利铮
王志杰
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Shanghai 800 Million Spacetime Advanced Material Co ltd
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Abstract

The invention relates to the technical field of organic electroluminescent materialsThe invention relates to a heterocyclic compound and application thereof. The structural formula of the heterocyclic compound is shown as a formula (I); the compound shown in the formula (I) has a phenanthridine 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 DDA0003912651260000011

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, the organic light emitting phenomenon refers to a phenomenon in which light is emitted 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 into the organic layer and electrons are injected from the cathode into 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 technologies have become mature, some products have entered the market, but many problems still need to be solved in the industrialization process. In particular, various organic materials used for manufacturing elements have many problems which are not solved, such as carrier injection and transmission performance, electroluminescent performance of the materials, service life, color purity, matching between various materials and between various electrodes, and the like; in particular, as a substance applied to an electron injection layer and a transport layer, the earliest reports on an electron transport material include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and typical substances for an electron transport layer having an imidazole group described in patent CN107573328A, CN107556310A, CN113801066A, CN113429395A, CN113429348A, CN114560872a and the like, and the substance has a structure containing an N-phenylbenzimidazole group, and has a function of not only transporting electrons but also blocking holes crossing from a light-emitting layer, but has a problem of low thermal stability when applied to an actual device.
In order to overcome the above-described problems and to further improve the characteristics of the organic electroluminescent element, development of a more stable and effective substance that can be used as an electron injecting and transporting substance in the organic electroluminescent element is continuously required.
In view of the above, the present invention is particularly proposed.
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 using the heterocyclic compound can obviously reduce the driving voltage, improve the luminous efficiency and prolong the service life; the invention also aims to provide application of the compound.
Specifically, the invention provides the following technical scheme:
the present invention provides a heterocyclic compound having a heterocyclic ring structure, the structural formula is shown as the formula (I):
Figure BDA0003912651240000011
wherein, the first and the second end of the pipe are connected with each other,
L 1 selected from the group consisting of single bonds substituted or unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 Heteroarylene group;
X 3 ～X 6 each independently of the other earth is CR 2 Or N;
X 1 and X 2 Represents a group of formula (II) or (III);
Figure BDA0003912651240000021
a represents, identically or differently on each occurrence, CR 3 Or N, and "^" indicates adjacent group X in formula (I) 1 And X 2 ；
G represents O, S or NR 4 ；
R 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile group, nitro group, carboxyl group or carboxylate thereof, sulfonic group or sulfonate thereof, phosphoric group or phosphate thereof, and 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 group, substituted or unsubstituted amine group, substituted or unsubstituted aryl phosphine group, substituted or unsubstituted phosphine oxide group, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; any adjacent two or more substituents may be optionally joined or fused to form a substituted or unsubstituted ring;
Ar 1 selected from 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 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups.
In the present invention, the "ring" refers to a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring in which adjacent groups are bonded to each other to form a substituted or unsubstituted ring. The condensed ring is 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 chemical formula (I), wherein the phenanthridine derivative containing nitrogen and the heterocycle containing the formula (II) or (III) are substituted by an arylene group or a heteroarylene group L 1 Combine to form a basic skeleton. The compound represented by the formula (I) of the present invention is electrochemically stable and has excellent electron mobility, and has a high glass transition temperature and excellent thermal stability, as compared with conventionally known phenanthridine heterocyclic structures. Accordingly, the heterocyclic compound of the present invention is excellent in electron transport ability and light emission characteristics, 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 an electron injection layer of an organic electroluminescent device. A material that can be used as any one of the light-emitting layer, the electron transport layer, and the electron transport assisting layer that is laminated in one step on the electron transport layer is preferable, and a material that can be used as the electron transport layer or the electron transport assisting layer is more preferable.
Specifically, the compound of the present invention, represented by formula (I), comprises a phenanthridine derivative containing two, three or four nitrogens and a heterocyclic compound containing formula (II) or formula (III), thereby having a stronger electron transport ability, and being capable of exhibiting a relatively high luminous efficiency and a high glass transition temperature, compared to a phenanthridine derivative containing one nitrogen, which has a weak electron withdrawing group ability. Accordingly, when the heterocyclic compound represented by formula (I) of the present invention is used in an organic electroluminescent device, not only excellent thermal stability and carrier transport ability, particularly electron transport ability and light-emitting ability, but also a reduction in driving voltage of the device, an improvement in efficiency and lifetime, and the like can be expected, and an excellent increase in efficiency due to a triplet-triplet fusion effect can be exhibited as a new electron transport layer material due to a high triplet level.
Furthermore, the heterocyclic compound represented by the formula (I) of the present inventionBy introducing various substituents R into the basic skeleton formed by phenanthridine derivatives containing nitrogen and containing compounds of formula (II) or (III) 1 、R 2 And R 3 The HOMO and LUMO levels are adjusted according to the kind of the substituent, so that the organic electroluminescent element can have a wide band gap and can exhibit the highest electron transport property in the organic electroluminescent element using such a compound.
Further, the heterocyclic compound represented by the formula (I) of the present invention is obtained by introducing various substituents L to the above basic skeleton 1 And Ar 1 Particularly aryl and/or heteroaryl, the molecular weight of the compound is significantly increased, and the glass transition temperature is increased, thereby enabling higher thermal stability than conventional light-emitting materials, such as phenanthridine. Therefore, the performance and life characteristics of an organic electroluminescent element comprising the compound according to the present invention can be greatly improved. The organic electroluminescent element with improved performance and life characteristics can finally maximize the performance of a full-color organic light-emitting panel.
In the heterocyclic compound represented by the formula (I) of the present invention, X of a phenanthridine derivative containing nitrogen 3 To X 6 Are the same or different from each other and are each independently N or CR 2 . At this time, preferably, the heterocyclic compound is selected from the group consisting of the following structures:
Figure BDA0003912651240000031
Figure BDA0003912651240000041
Figure BDA0003912651240000051
Figure BDA0003912651240000061
wherein R is 1 、R 2 、R 3 Each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, methyl, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, triphenylene, carbazolyl, fluorenyl, dibenzofuran, or dibenzothiophene.
Preferably, R is 1 、R 2 、R 3 Each independently hydrogen or phenyl.
As a preference, the first and second liquid crystal compositions are, and G is O or S.
Preferably, ar is 1 Selected from phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, pyrenyl,
Figure BDA0003912651240000072
A phenyl group, a perylene group, a fluoranthenyl group, a tetracenyl group, a pentacenyl group, a benzopyrenyl group, a biphenyl group, an idophenyl group, a terphenyl group, a fluorenyl group, a spirobifluorenyl group, a dihydrophenanthryl group, a triphenylene group, a dihydropyrenyl group, a tetrahydropyrenyl group, a cis-or trans-indenofluorenyl group, a cis-or trans-indenocarbazolyl group, an indolocarbazolyl group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an azadibenzo [ g, ij ] group]Naphtho [2,1,8-cde]Azulene, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo [5,6]Quinolyl, benzo [6,7]Quinolyl, benzo [7,8]<xnotran> , , , , , , , , , , , , , , , , , , 5363 zxft 5363- , 3242 zxft 3242- , , , , , , , , 4736 zxft 4736- , 8978 zxft 8978- , 6253 zxft 6253- </xnotran>1,6-diazpyrenyl, 1,8-diazpyrenyl, 4,5-diazpyrenyl, 4,5,9,10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorrycyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, carbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, and thiadiazolyl 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 a combination derived from these systems.
In the heterocyclic compound represented by the formula (I) of the present invention, ar 1 May be selected from the group consisting of generally known electron withdrawing groups. At this time, ar is 1 Preferably selected from the group consisting of the following groups II-1 to II-17:
Figure BDA0003912651240000071
wherein the content of the first and second substances,
Z 1 、Z 2 each independently selected from hydrogen, deuterium, halogen, hydroxy nitrile group, nitro group, amino group, amidino group, hydrazine group hydrazone group, carboxyl group or carboxylate thereof, sulfonic group or sulfonate thereof, phosphoric group or phosphate thereof, C 1 -C 40 Alkyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 3 -C 40 Cycloalkenyl radical, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylthioether group, substituted or unsubstituted C 6 -C 60 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl 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 denotes O, S, CR ’ R ” Or NAr ’ ；
R ’ 、R ” Each independently selected from hydrogen, deuterium, C 1 ～C 40 Alkyl of (C) 1 ～C 40 With heteroalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Arylamino, or substituted or unsubstituted C 2 -C 60 Group consisting of heterocyclic aryl radicals, R ’ And R ” 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 ’ 、R ” Is methyl, phenyl or fluorenyl;
Ar ’ selected from the group consisting of C 1 ～C 40 Alkyl of (C) 1 ～C 40 Heteroalkyl of (a), 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 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; preferably, ar ’ Is methyl, ethyl, phenyl, biphenyl or naphthyl;
Figure BDA0003912651240000081
to represent Ar (Ar) 1 And L 1 The groups represented by the above formulas II-1 to II-17 may be independently selected from deuterium, a halogen atom, a nitrile group, a nitro group and C 1 -C 40 Alkyl radical, C 2 -C 40 An alkenyl group C 2 -C 40 Alkynyl, C 3 -C 40 Cycloalkyl radical, C 3 -C 40 Heterocycloalkyl radical, C 6 -C 60 Aryl and C 2 -C 60 Heterocyclic aryl radicals, C 1 -C 40 Alkoxy radical, C 6 -C 60 Aryloxy radical, C 1 -C 40 Alkylsilyl group, C 6 -C 60 Aryl silyl group, C 1 -C 40 Alkyl boron radical, C 6 -C 60 Arylboron radical, C 6 -C 60 Aryl phosphine group, C 1 -C 60 Aryl phosphine oxide group and C 6 -C 60 When the substituent is plural, it is preferable that plural substituents are the same as or different from each other.
In the heterocyclic compound represented by the formula (I) of the present invention, L 1 Is prepared by reacting the above-mentioned nitrogen-containing phenanthridine derivative with the above-mentioned Ar 1 The attached functional group may be selected from the group consisting of C 6 -C 60 Arylene group of (A) and C 2 -C 60 Group of heteroarylene groups. At this time, preferably, L is 1 Selected from a single bond or a group consisting of the following groups III-1 to III-23:
Figure BDA0003912651240000082
wherein the dotted line represents the linking site of the group, and in this case, the binding site of the group represented by the above formulas III-1 to III-23 is not limited, and may be ortho, meta, or para. L mentioned above 1 Can be independently selected from deuterium, halogen atom, nitrile group and C 1 -C 40 Alkyl radical, C 6 -C 60 Aryl and C 2 -C 60 When the substituent is plural, it is preferable that plural substituents are the same as or different from each other.
The term "substituted or unsubstituted" as used herein means a group 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 radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl, C 3 -C 40 Cycloalkenyl radical, C 6 -C 60 Aryl radical, C 6 -C 60 Aryloxy radical, C 6 -C 60 An arylsulfonyl group and C 2 -C 60 The heterocyclic aryl group may be substituted or unsubstituted with 1 or more substituents, or may be substituted or unsubstituted with substituents formed by connecting 2 or more substituents among the above-exemplified substituents.
Aryl in the sense of the present invention contains 6 to 60 carbon atoms and heteroaryl contains 2 to 60 carbon atoms and at least one heteroatom, with the proviso 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, and further, may include a form condensed with the aryl group. As non-limiting examples of such heteroaryl groups, six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; polycyclic rings such as phenoxathiyl, indolizinyl, indolyl, purinyl, quinolinyl, benzothiazolyl, carbazolyl, and the like; and 2-furyl, N-imidazolyl, 2-isoxazolyl, 2-pyridyl, 2-pyrimidyl and the like.
Alkyl in the sense of the present invention contains 1 to 40 carbon atoms and wherein the individual hydrogen atoms or-CH 2 -a linear alkyl group or an alkyl group with a branched chain, the groups of which may also be substituted; alkenyl or alkynyl groups contain at least two carbon atoms, and as non-limiting examples, alkyl, alkenyl or alkynyl groups are preferably considered to refer to 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, preferably alkoxy having from 1 to 40 carbon atoms, is to be understood as meaning methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexoxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy.
Heteroalkyl is preferably alkyl having 1 to 40 carbon atoms, meaning that the individual hydrogen atoms or-CH 2 The radicals substituted by oxygen, sulfur or halogen atoms, alkoxy, alkylthio, fluorinated alkoxy, fluorinated alkylthio, 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, 2,2,2-trifluoroethoxy, 2,2,2-trifluoroethylthio, vinyloxy, propenyloxy, propenylthio, butenyloxy, pentenyloxy, pentenylthio, cyclopentenyloxy, cyclopentenylthio, hexenyloxy, hexenylthio, cyclohexenyloxy, cyclohexenylthio, ethynyloxy, ethynylthio, propynyloxy, propynylthio, butynyloxy, butynylthio, pentynyloxy, pentynylthio, hexynyloxy, hexynylthio, as non-limiting examples.
In general, the cycloalkyl, cycloalkenyl groups according to the invention may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, where one or more-CH may be present 2 The radicals may be replaced by the radicals mentioned above; furthermore, one or more hydrogen atoms may also be replaced by deuterium atoms, halogen atoms or nitrile groups.
The heterocycloalkyl group used in the present invention refers to a monovalent functional group obtained by removing one hydrogen atom from a non-aromatic hydrocarbon having an atomic number of 3 to 40. At this point, more than one carbon, preferably 1 to 3 carbons, in the ring is substituted with a heteroatom such as N, O or S. As non-limiting examples thereof, there are tetrahydrofuran, tetrahydrothiophene, morpholine, piperazine and the like.
The inventionThe fused ring aryl group used in (1) is a monovalent functional group obtained by combining two or more rings of an aromatic hydrocarbon having 6 to 60 carbon atoms and removing one hydrogen atom. In this case, two or more rings may be attached to each other simply or in a condensed form. As non-limiting examples thereof, may be mentioned phenanthryl, anthracyl, fluoranthyl, pyrenyl, triphenylenyl, perylenyl, perylene, etc,
Figure BDA0003912651240000091
And the like.
The arylamine group used in the present invention means an amine substituted with an aryl group having 6 to 60 carbon atoms, and non-limiting examples of the arylamine group include a diphenylamine group, an N-phenyl-1-naphthylamine group, an N- (1-naphthyl) -2-naphthylamine group and the like. The heteroarylamine 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 heteroarylamine group, there are N-phenylpyridin-3-amine group, N- ([ 1,1 '-biphenyl ] -4-yl) dibenzo [ b, d ] furan-2-amine group, N- ([ 1,1' -biphenyl ] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine group, and the like.
Alkoxy as used herein means RO - The monovalent functional group represented by R is an alkyl group having 1 to 40 carbon atoms and may have a linear, branched or cyclic structure. Non-limiting examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentyloxy, cyclopentyloxy, cyclohexyloxy, and the like.
Aryloxy as used in the present invention means R' O - The monovalent functional group represented by 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 non-limiting examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, and the like. The arylsilyl group means a silyl group substituted with an aryl group having 6 to 60 carbon atoms.
The aryl phosphorus group used in the present invention means a diaryl phosphorus group substituted with an aryl group having 6 to 60 carbon atoms, and non-limiting examples of the aryl phosphorus group include a diphenyl phosphorus group, a bis (4-trimethylsilylphenyl) phosphorus group and the like. The aryloxyphosphorus group is a group in which the phosphorus atom of the diarylphosphorus group is oxidized to the highest valence state.
The arylboron group used in the present invention means a diarylboron group substituted with an aryl group having 6 to 60 carbon atoms, and non-limiting examples of the arylboron group include a diphenylboron group, a bis (2,4,6-trimethylbenzene) boron group, and the like. The alkyl boron group means a dialkyl boron group substituted with an alkyl group having 1 to 40 carbon atoms, and non-limiting examples of the alkyl boron group include a di-t-butyl boron group, a diisobutyl boron group and the like.
Further, the aryl, heteroaryl or heterocyclic aryl group is preferably selected from the group consisting of phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, pyrenyl,
Figure BDA0003912651240000102
A phenyl group, a perylene group, a fluoranthenyl group, a tetracenyl group, a pentacenyl group, a benzopyrenyl group, a biphenyl group, an idophenyl group, a terphenyl group, a fluorenyl group, a spirobifluorenyl group, a dihydrophenanthryl group, a triphenylene group, a dihydropyrenyl group, a tetrahydropyrenyl group, a cis-or trans-indenofluorenyl group, a cis-or trans-indenocarbazolyl group, an indolocarbazole group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an azadibenzo [ g, ij ] group]Naphtho [2,1,8-cde]Azulene, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo [5,6]Quinolyl, benzo [6,7]Quinolyl, benzo [7,8]Quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, quinoxalyl pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, 12-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazatriphenylenyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazenanthrenyl, 2,7-diazpyrenyl, 2,3-diazpyrenyl, 1,6-diazpyrenyl, 1,8-diazpyrenyl, 4,5-diazpyrenyl, 3575-tetraazaperylenyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorheterocyclyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, carbolinyl, phenanthrolinyl, 3625 zxft 3525-triazolyl, 1,2,4-triazolyl, hexaazapyrenyl, phenanthrolinyl, quinoxalinyl, phenanthrolinyl, naphthyridinyl, azacarbazolyl, benzocarbinyl, carbolinyl, phenanthrolinyl, 3625 zxft 3525-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-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 a group derived from a combination of these systems.
Preferably, the heterocyclic compound is selected from compounds represented by the following formula J475-J600:
Figure BDA0003912651240000101
Figure BDA0003912651240000111
Figure BDA0003912651240000121
Figure BDA0003912651240000131
Figure BDA0003912651240000141
Figure BDA0003912651240000151
Figure BDA0003912651240000161
wherein the content of the first and second substances,
*—T 3 -is selected from-O-, -S-, or one of the following structures:
Figure BDA0003912651240000162
* -and-represent a connecting bond.
The present invention also provides a method for preparing the heterocyclic compound described above, as shown in scheme 1:
in the case of the scheme 1,
Figure BDA0003912651240000163
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 from commercial sources, the method principle, the operation process, the conventional post treatment, the column purification, the recrystallization purification and other means are well known by the synthesizers in the field, and the synthesis process can be completely realized to obtain the target product.
Specifically, the compound of formula (I) is prepared by carrying out coupling substitution reaction on O-nitrile halogenated S0 and alkyne to prepare an intermediate S1; the intermediate S1 and nitromethane are subjected to ring closure to prepare an intermediate S2; diazotizing S2 with amino to prepare a halogenated intermediate S3 of o-nitro; intermediate S3 and ortho R 1 The boric acid of the formyl group or the boric acid pinacol ester is subjected to SUZUKI coupling reaction to prepare a compound S4, and the carbonyl group of the compound S4 and the nitro group are subjected to condensation reaction to prepare the compound shown in the formula (I). Intermediate Ar 1 -L 1 -Y and alkynes thereofThe derivatives are prepared by palladium-catalyzed or base-catalyzed coupling reactions.
As palladium catalysts which may be used in the palladium-catalyzed coupling reaction, there may be selected: pd (P- t Bu 3 ) 2 、Pd(PPh 3 ) 4 、Pd 2 (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)Cl] 2 And the like, or a mixture of two or more thereof is used.
In addition, the base used in the palladium-catalyzed coupling reaction or base-catalyzed coupling reaction may be selected from: sodium tert-butoxide, potassium tert-butoxide, sodium hydride, lithium hydride, sodium tert-amylate, 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: ether solvents such as diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, ethylene glycol ethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ether, diethylene glycol diethyl ether, or anisole, aromatic hydrocarbon solvents such as benzene, toluene, or xylene, chlorobenzene, dichlorobenzene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane, and one kind or a mixture of two or more kinds thereof can be used.
The invention also provides an organic electroluminescent material, the raw material of which comprises the heterocyclic compound; the organic electroluminescent material comprising the heterocyclic compound of the present invention has a carrier transport ability.
The invention also provides the application of the heterocyclic compound in the preparation of organic electroluminescent elements.
The present invention also provides an organic electroluminescent element comprising: the organic light-emitting diode comprises a first electrode, a second electrode, a capping layer and more than one organic layer arranged 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 includes 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-injecting layers, hole-transporting layers, hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking layers, electron-blocking layers and/or charge-generating layers. An intermediate layer having, for example, exciton blocking function can likewise be introduced between the two light-emitting layers. However, it should be noted that each of these layers need not be present. The organic electroluminescent device described herein may include one light emitting layer, or it may include 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. Particular preference is given to systems having three light-emitting layers, where the three layers can exhibit blue, green and red emission. If more than one light-emitting layer is present, at least one of these layers comprises, according to the invention, a heterocyclic compound according to the 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 the hole-transporting layer or the anode and/or the light-emitting layer is directly adjacent to the electron-transporting layer or the electron-injecting layer or the cathode.
In the other layers of the organic electroluminescent element according to the invention, in particular in the hole-injecting and hole-transporting layer and in the electron-injecting and electron-transporting layer, all materials can be used in the manner conventionally used according to the prior art. The person skilled in the art will thus be able to use all materials known for organic electroluminescent elements in combination for the light-emitting layer according to the invention without inventive effort.
Preference is furthermore given to organic electroluminescent elements in which one or more layers are applied by means of a sublimation process in which the temperature in a vacuum sublimation apparatus is below 10 -5 Pa, a preferably below 10 -6 Pa is applied by vapor deposition. However, the aboveThe initial pressure may also be even lower, e.g. 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 10 is -5 The material is applied under a pressure between Pa and 1 Pa. A particular example of this method is the organic vapour jet printing method, in which the material is applied directly through a nozzle and is therefore structured.
Preference is furthermore given to organic electroluminescent elements in which one or more layers are produced from solution, for example by spin coating, or by means of any desired printing method, for example screen printing, flexographic printing, offset printing, photoinitiated thermal imaging, thermal transfer, ink-jet 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, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.
These methods are generally known to those skilled in the art, and they can be applied to an organic electroluminescent element comprising the compound according to the present invention without inventive labor.
The invention therefore also relates to a method for producing 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 vapor 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 a composition comprising at least one of the above-indicated heterocyclic compounds of the present invention. The same preferences as indicated above for the organic electroluminescent elements apply to the compounds according to the invention. In particular, it is preferable that other compounds may be contained in addition to the heterocyclic compound. Processing the heterocyclic compounds of the invention from the liquid phase, for example by spin coating or by printing methods, requires the processing of the formulations of the compounds of the invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferred to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchytone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α -terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phene, 3835-diisopropylbenzene, dibenzyl ether, diethylbutylmethylbutyl methyl ether, diethylbutylmethylbutylmethylbutylmethylnaphthalene, triethylmethylnaphthalene, isopropylbenzene ether, 3534-diethylbutylmethylnaphthalene, isopropylbenzene ether, 3534-dimethylbenzene ether, 3534-diisopropylbenzene, diethylbutylglycol, triethylbenzene, isopropylbenzene, 3534-diol, triethylbenzene glycol, or mixtures of these.
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.
The invention also provides a consumer product comprising the organic electroluminescent element.
In addition, unless otherwise specified, all starting materials for use in the present invention are commercially available, and any range recited herein includes any value between the endpoints and any subrange between the endpoints and any value between the endpoints or any subrange between the endpoints.
The invention has the following beneficial effects:
the heterocyclic compound represented by the formula (I) provided by the invention is excellent in electron mobility, thermal stability and light-emitting characteristics, and thus can be applied to an organic layer of an organic electroluminescent element. In particular, when the heterocyclic compound represented by the formula (I) of the present invention is used in an electron transporting layer and an electron transporting auxiliary layer, an organic electroluminescent element having a lower driving voltage, higher efficiency and longer lifetime than those of conventional electron transporting materials can be produced, and furthermore, 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 layer 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 described layers.
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 layer 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 layer 213. The device 200 may be prepared by sequentially depositing the described layers. Since the most common OLED devices have one light emitting layer, while device 200 has a first light emitting layer and a second light emitting layer, the light emitting peak shapes of the first light emitting layer and the second light emitting layer may be overlapping or cross-overlapping or non-overlapping. In the corresponding layers of the device 200, materials similar to those described with respect to the device 1 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 intended to illustrate the invention but are not intended to limit the scope of the invention.
In the description of the present invention, "a plurality" means two or more unless otherwise specified; the terms "upper", "lower", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the referred devices or elements must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The experimental raw materials and the related equipments used in the following examples are commercially available unless otherwise specified, and the percentages are by mass unless otherwise specified.
The following examples are provided for testing the performance of OLED materials and devices using the following test apparatus and method:
OLED element performance detection conditions:
luminance and chromaticity coordinates: testing with a photosresearch PR-715 spectrum scanner;
current density and lighting voltage: testing using a digital source table Keithley 2420;
power efficiency: tested using NEWPORT 1931-C.
Example 1
A process for the preparation of compound J475, comprising the steps of:
the first step is as follows: preparation of intermediate Int-1
Figure BDA0003912651240000191
Under the protection of nitrogen, 20.0mmol of o-iodobenzonitrile is dissolved in 60mL of triethylamine, and 22.0mmol of p-chlorophenyl acetylene, 2.0mmol of cuprous iodide and 0.2mmol of PdCl are added 2 (PPh 3 ) 2 And (3) stirring the catalyst to react for 12 hours, filtering, concentrating the filtrate under reduced pressure, and separating and purifying by a silica gel column to obtain an intermediate Int-1 with the yield of 93%.
The second step is that: preparation of intermediate Int-2
Figure BDA0003912651240000192
Under the protection of nitrogen, 50.0mmol of Int-1 is dissolved in 80mL of DMSO, 0.1mol of nitromethane and 0.1mol of potassium hydroxide are added, the temperature is raised to 110 ℃, the mixture is stirred and reacted for 1 hour, the temperature is reduced to room temperature, 150mL of saturated sodium bisulfite aqueous solution is added, extraction is carried out by ethyl acetate, organic phase drying, filtration, concentration and drying under reduced pressure are carried out, and separation and purification are carried out by an alumina column, so as to obtain orange solid, and the yield: 86 percent.
The third step: preparation of intermediate Int-3
Figure BDA0003912651240000193
Under the protection of nitrogen, dissolving 20.0mmol of Int-2 in 50mL of acetonitrile, adding 40mL of 48% hydrobromic acid and 40mL of water, cooling to 0 ℃ in an ice bath, slowly dropwise adding a solution of 24.0mmol of sodium nitrite in water, stirring for reaction for 1 hour, adding 24.0mmol of cuprous bromide in batches, heating to room temperature, stirring for reaction for 2 hours, extracting with ethyl acetate, washing an organic phase with saturated saline, collecting the organic phase, drying, filtering, concentrating the filtrate under reduced pressure, and separating and purifying by using a silica gel column to obtain yellow solid Int-3, wherein the yield is: 73 percent.
The fourth step: preparation of intermediate Int-4
Figure BDA0003912651240000194
Under the protection of nitrogen, 20.0mmol of Int-3, 22.0mmol of 2-aldehyde phenylboronic acid pinacol ester, 36.0mmol of anhydrous sodium carbonate and 40mL of toluene are mixed, 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, the mixture is cooled to room temperature, 50mL of water is added for dilution, dichloromethane is used for extraction, an organic phase is collected, dried, filtered, filtrate is subjected to reduced pressure concentration, and is separated and purified by a silica gel column, so that a compound Int-4 is obtained, and the yield is 76%.
The fifth step: preparation of intermediate A1
Figure BDA0003912651240000201
Under the protection of nitrogen, mixing 20.0mmol of Int-4 with 50mL of glacial acetic acid, heating to 100 ℃, adding 60.0mmol of iron powder in batches, heating to reflux, stirring for reaction for 2 hours, cooling to room temperature, filtering, concentrating the filtrate under reduced pressure, adding 100mL of ethyl acetate for dissolution, washing with water, drying the organic phase, filtering, concentrating the filtrate under reduced pressure, and separating and purifying by using a silica gel column to obtain a compound A1 which is a light yellow solid with the yield of 82%.
With reference to the analogous synthetic procedures described above, the following compounds were prepared:
Figure BDA0003912651240000202
Figure BDA0003912651240000211
Figure BDA0003912651240000221
Figure BDA0003912651240000231
and a sixth step: preparation of intermediate Int-6
Figure BDA0003912651240000241
Under the protection of nitrogen, 20.0mmol of A1 is dissolved in 60mL of dry DMF, and 24.0mmol of pinacol diboron, 30.0mmol of anhydrous potassium acetate and 0.2mmol of PdCl are added 2 (dppf) and 2.0mmol cuprous iodide, heating to 100 ℃, stirring for reaction for 12 hours, cooling to room temperature, pouring the reaction solution into 120mL of water, filtering, washing a filter cake with water, drying, and separating and purifying by using a silica gel column to obtain a white solid, wherein the yield is as follows: and 78 percent.
The seventh step: preparation of Compound J475
Figure BDA0003912651240000242
Under the protection of nitrogen, 12.0mmol of intermediate Int-6, 10.0mmol of 2-chloro-4,6-diphenyl-1,3,5-triazine, 36.0mmol of anhydrous potassium carbonate and 40mL of toluene are mixed, 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, the mixture is cooled to room temperature, 50mL of water is added for dilution, dichloromethane is used for extraction, an organic phase is collected, dried and filtered, filtrate is concentrated under reduced pressure to dryness, and is separated and purified by a silica gel column to obtain compound J475, white solid with the yield of 76%, MS (MALDI-TOF): m/z =537.2095[ m ] +H] + ； 1 HNMR(δ、CDCl 3 )：9.35(1H,s)；8.76～8.69(7H,m)；8.57～8.53(2H,m)；8.25～8.20(3H,m)；8.04～8.01(1H,m)；7.78～7.63(4H,m)；7.55～7.51(4H,m)；7.45～7.41(2H,m)。
With reference to the above synthetic method, the following compounds shown in table 1 were prepared:
TABLE 1
Figure BDA0003912651240000243
Figure BDA0003912651240000251
Figure BDA0003912651240000261
Figure BDA0003912651240000271
Figure BDA0003912651240000281
Example 2
A process for the preparation of compound J552, comprising the steps of:
the first step is as follows: preparation of intermediate Int-7
Figure BDA0003912651240000291
Referring to the first synthesis step of example 1, intermediate Int-7 was prepared in 87% yield by replacing SM-1 with SM-2 and p-chlorophenylacetylene with o-chlorophenylacetylene in the first step of example 1.
The second step is that: preparation of intermediate Int-8
Figure BDA0003912651240000292
Referring to the synthesis method of the second step of example 1, int-8, an intermediate, was prepared in 87% yield by replacing Int-1 with Int-7 in the second step of example 1.
The third step: preparation of intermediate Int-9
Figure BDA0003912651240000293
Referring to the synthesis procedure of the third step of example 1, int-2 in the third step of example 1 was replaced with Int-8 to prepare an intermediate Int-9 with a yield of 75%.
The fourth step: preparation of intermediate Int-10
Figure BDA0003912651240000294
Referring to the fourth step of the synthesis of example 1, intermediate Int-10 was prepared in 74% yield by replacing Int-9 with Int-3 only in the fourth step of example 1.
The fifth step: preparation of intermediate Int-11
Figure BDA0003912651240000295
Referring to the synthesis procedure of the fifth step of example 1, intermediate Int-11 was prepared in 81% yield by replacing Int-10 with Int-4 only in the fifth step of example 1.
And a sixth step: preparation of Compound J552
Figure BDA0003912651240000296
12.0mmol of intermediate Int-11, 10.0mmol of 15H-azepine [2,3,4,5-def:6,7,1-j ' k ' under nitrogen protection ']Dicarbazole, 15.0mmol of sodium tert-butoxide, 0.01mmol of Pd 2 (dba) 3 The catalyst, 0.04mmol of 10% tri-tert-butylphosphine toluene solution and 50mL of xylene are heated to 110 ℃ and stirred to react for 12 hours, the temperature is reduced to room temperature, 50mL of water is added to dilute the reaction solution, dichloromethane is used for extraction, an organic phase is collected, the drying and the filtration are carried out, the filtrate is decompressed and concentrated, and a silica gel column is used for separation and purification to obtain a compound J552, a yellow solid with the yield of 78%, MS (MALDI-TOF): m/z =636.2206[ M + H ]] + ； 1 HNMR(δ、CDCl 3 )：9.38(1H,s)；9.35(1H,s)；9.27(1H,s)；9.13～9.10(2H,m)；8.51～8.48(1H,m)；8.41～8.32(4H,m)；8.26～8.18(3H,m)；8.09～8.01(3H,m)；7.92～7.87(1H,m)；7.64～7.62(1H,m)；7.55～7.52(1H,m)；7.49～7.36(4H,m)；7.33～7.26(2H,m)。
With reference to the analogous synthetic procedures described above, the following compounds shown in table 2 were prepared:
TABLE 2
Figure BDA0003912651240000301
Figure BDA0003912651240000311
Figure BDA0003912651240000321
In the above embodiment, - [ T ] 3 -is selected from-O-, -S-, or one of the structures shown below:
Figure BDA0003912651240000322
* -and-represent a connecting bond.
Example 3
An OLED element, as shown in fig. 1, the OLED element of this 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 layer 110 disposed on the electron injection layer 109 and a capping layer 111 disposed on the cathode layer, and the method for manufacturing the OLED element without 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, washed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked to be completely dry in a clean environment, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the processed ITO glass substrate in a vacuum chamber, and vacuumizing to less than 1 × 10 -5 Pa, depositing silver on the ITO film as anode layer to obtain a deposited film with a thickness of
Figure BDA0003912651240000332
Continuing to respectively evaporate HI01 and F4TCNQ as hole injection layers, wherein F4TCNQ is 3% of HI01 by mass, and the thickness of the evaporated film is
Figure BDA0003912651240000333
3) Continuously depositing a compound HTM on the hole injection layer to form a hole transport layer, wherein the deposition film has a thickness of
Figure BDA0003912651240000334
4) Continuously depositing a compound EBL on the hole transport layer to form an electron blocking layer with a thickness of
Figure BDA0003912651240000335
5) The compound represented by the formula (I) of the present invention as a host material and RD11 as a dopant material were further deposited on the electron blocking layer, the amount of RD11 being 3% of the amount of the compound represented by the formula (I), and the organic light-emitting layer was formed as an organic light-emitting layer of the device, and the thickness of the organic light-emitting layer obtained by deposition was set to be a film thickness
Figure BDA0003912651240000336
6) Continuously evaporating a LiQ layer and a compound ET025 layer on the organic light-emitting layer to form an electron transport layer of the device, wherein the mass of the compound ET025 is 50% of that of the LiQ layer, and the thickness of the evaporated film is
Figure BDA0003912651240000337
7) Continuously evaporating a layer of LiF on the electron transport layer to form an electron injection layer, wherein the thickness of the evaporated film is
Figure BDA0003912651240000338
8) And depositing 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
Figure BDA0003912651240000339
9) A CPL layer serving as an element is deposited on the transparent cathode layer by evaporation to a thickness of
Figure BDA00039126512400003310
To obtainThe invention provides an OLED element.
The compound used in example 3 above has the following structure:
Figure BDA0003912651240000331
example 4
An organic electroluminescent device 200 is shown in fig. 2, and comprises a substrate 201, an anode layer 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 layer 213.
Comparative example 1
Following the same procedure as in example 3, substituting the compound of formula (I) in step 5) with H01 gave comparative element 1;
Figure BDA0003912651240000341
comparative example 2
Following the same procedure as in example 3, substituting the compound of formula (I) in step 5) with H02, comparative element 2 was obtained;
Figure BDA0003912651240000342
comparative example 3
Following the same procedure as in example 3, the compound of formula (I) in step 5) was replaced with H03 to give comparative element 3;
Figure BDA0003912651240000343
comparative example 4
Following the same procedure as in example 3, the compound of formula (I) in step 5) was replaced with H04 to give comparative element 4;
Figure BDA0003912651240000344
the organic electroluminescent element prepared by the above process was subjected to the following performance tests:
the driving voltage and current efficiency of the organic electroluminescent elements prepared in examples 3 and 4 and comparative examples 1 to 4 and the lifetime of the elements were measured using a digital source meter and a luminance meter. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent element reached 1000cd/m 2 The current voltage is the driving voltage, and the current density at the moment is measured; the ratio of the brightness to the current density is the current efficiency; the LT95% lifetime test is as follows: using a luminance meter at 1000cd/m 2 The luminance degradation of the organic electroluminescent element was measured to 950cd/m while maintaining a constant current at luminance 2 Time in hours. The data listed in table 3 are relative data compared to comparative element 1.
TABLE 3
Figure BDA0003912651240000345
Figure BDA0003912651240000351
Figure BDA0003912651240000361
Figure BDA0003912651240000371
In the above table, ph is phenyl, phPh is biphenyl, nap is naphthyl, and FR is 9,9-fluorenyl.
As can be seen from table 3, the device prepared from the heterocyclic compound of the present invention has a lower driving voltage compared to H01 at the same brightness, the current efficiency is improved significantly, which is up to 1.3 times that of the comparative device, and the LT95% lifetime of the device is greatly improved.
Compared with the compound of the invention, the compound H01 in the comparative example 1 is different in that the planar conjugation capability is weak after a substituent group is introduced at the ortho-position of phenanthridine nitrogen, so that the voltage is high and the efficiency is low. The compound of the invention has strong conjugation ability of introducing substituent groups on benzene rings, has more excellent performances on molecular film formation and charge transmission, and the charge transmission in elements is more balanced, so the element performance is obviously improved.
The compound H02 in comparative example 2 is different from the compound of the present invention in that phenanthridine incorporates a phenyl group, and although the planar conjugation ability is enhanced, steric hindrance increases, and molecular film formation and charge transport properties decrease, resulting in high voltage and reduced efficiency. The compound of the invention increases the conjugated plane and reduces the steric hindrance, so the compound has more excellent performance on molecular film formation and charge transmission, and the charge transmission in the element is more balanced, thereby the element performance is obviously improved.
Compared with the compound of the invention, the compound H03 in the comparative example 3 is different from the compound of the invention in that phenanthridine is combined with a phenyl group, and a phenyl group is introduced at the ortho position of nitrogen, so that although the plane conjugation capacity is enhanced, the steric hindrance is increased, the molecular film forming and charge transmission performance is reduced, and the voltage is high, and the efficiency is reduced. The compound of the invention introduces substituent groups at the same side of nitrogen, but does not introduce the substituent groups to the ortho position of the nitrogen, so that the steric hindrance is reduced while the conjugated plane is increased, therefore, the compound has more excellent performances on molecular film formation and charge transmission, and the charge transmission in the element is more balanced, thereby the element performance is obviously improved.
Compared with the compound of the invention, the compound H04 in the comparative example 4 is different in that two electron-withdrawing groups are introduced on the basis of benzophenanthridine, so that the plane conjugation capability is reduced, the molecular film forming and charge transfer performances are reduced, and the voltage is high and the efficiency is reduced. The compound of the invention increases the conjugated plane of the parent nucleus, and simultaneously introduces electron-withdrawing groups or strong electron-donating groups on the benzene ring at the same side of nitrogen but not the ortho position to improve the electron transmission performance, so the compound has more excellent performance on molecular film formation and charge transmission, and the charge transmission in the element is more balanced, thereby the element performance is obviously improved.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A heterocyclic compound having a structural formula as shown in formula (I):
Figure FDA0003912651230000011
wherein the content of the first and second substances,
L 1 selected from the group consisting of single bonds, substituted or unsubstituted C 6 -C 60 Arylene, or substituted or unsubstituted C 2 -C 60 Heteroarylene;
X 3 ～X 6 each independently is CR 2 Or N;
X 1 and X 2 Represents a group of the following formula (II) or formula (III);
Figure FDA0003912651230000012
a represents, identically or differently on each occurrence, CR 3 Or N, and "^" indicates adjacent group X in formula (I) 1 And X 2 ；
G represents O, S or NR 4 ；
R 1 Selected from hydrogen, phenyl, biphenyl or pyridyl;
R 2 、R 3 、R 4 each independently selected fromHydrogen, deuterium, fluorine, hydroxyl, nitrile, nitro, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, and 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 group, substituted or unsubstituted amine group, substituted or unsubstituted aryl phosphine group, substituted or unsubstituted phosphine oxide group, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; any adjacent two or more substituents may be optionally joined or fused to form a substituted or unsubstituted ring;
Ar 1 selected from 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 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups.
2. The heterocyclic compound of claim 1, characterized in that the heterocyclic compound is selected from the group consisting of the following structures:
Figure FDA0003912651230000021
Figure FDA0003912651230000031
Figure FDA0003912651230000041
Figure FDA0003912651230000051
Figure FDA0003912651230000061
wherein R is 1 Selected from hydrogen or phenyl;
R 2 、R 3 each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, methyl, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, triphenylene, carbazolyl, fluorenyl, dibenzofuran, or dibenzothiophene.
3. The heterocyclic compound according to claim 2, wherein R is 1 、R 2 、R 3 Each independently is hydrogen or phenyl;
g is O or S;
Ar 1 selected from phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, pyrenyl,
Figure FDA0003912651230000062
A phenyl group, a perylene group, a fluoranthenyl group, a tetracenyl group, a pentacenyl group, a benzopyrenyl group, a biphenyl group, an idophenyl group, a terphenyl group, a fluorenyl group, a spirobifluorenyl group, a dihydrophenanthryl group, a triphenylene group, a dihydropyrenyl group, a tetrahydropyrenyl group, a cis-or trans-indenofluorenyl group, a cis-or trans-indenocarbazolyl group, an indolocarbazolyl group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an azadibenzo [ g, ij ] group]Naphtho [2,1,8-cde]Azulene,Trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo [5,6]Quinolyl, benzo [6,7]Quinolyl, benzo [7,8]Quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxaloimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthrenyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazanthronyl, 2,7-diazpyrenyl, 2,3-diazepinyl, 1,6-diazphynyl, 1,8-diazepinyl, 4,5-diazpyrenyl, 4,5,9,10-tetraazaperylenyl, pyrazinyl, phenazinyl, fluoresceinyl, naphthyridinyl, naphthyrinyl, 5427, 5428 zcarbazolyl, 358692-carbazolyl, 4235-oxadiazolyl, 32629692-oxadiazolyl, 326252-oxadiazolyl, 329658-diazepinyl, 359652-74ztft 359675-diazepinyl, 359675-piperazinyl, 325252-diazepinyl, 32529652-35ztft, 325252-diazepinyl, 325252-35ztft, 32529652-diazepinyl, 325252-35ztft, 325252-diazepinyl, 32529635-diazepinyl, 328652-35ztft, 325235-35ztft, 328652-piperazinyl, 32529635-35ztft, 32529652-a combination of such as a benzoxazolinyl, 32529635-piperazinyl, 32529635-35ztft, 328652-piperazinyl, 3252965-35ztft, and 328652-piperazinyl, 328652-35ztft.
4. The heterocyclic compound according to claim 1 or 3, characterized in that Ar is Ar 1 Selected from the group consisting of groups represented by II-1 to II-17:
Figure FDA0003912651230000071
wherein the content of the first and second substances,
Z 1 、Z 2 each independently selected from the group consisting of hydrogen, deuterium, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxy or carboxylate thereof, sulfonic or sulfonate thereof, phosphoric or phosphate thereof, C 1 -C 40 Alkyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy radical, C 3 -C 40 Cycloalkyl radical, C 3 -C 40 Cycloalkenyl radical, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 An arylthioether group, substituted or unsubstituted C 6 -C 60 Arylamino, or substituted or unsubstituted C 2 -C 60 Heterocyclic aryl 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 represents O, S, CR 'R "or NAr';
r 'and R' are each independently selected from hydrogen, deuterium, C 1 ～C 40 Alkyl of (C) 1 ～C 40 With heteroalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Arylamino, or substituted or unsubstituted C 2 -C 60 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 formed rings; preferably, R', R "are methyl, phenyl or fluorenyl;
ar' is selected from C 1 ～C 40 Alkyl of (C) 1 ～C 40 Heteroalkyl of (a), 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 Aromatic aminesOr substituted or unsubstituted C 2 -C 60 Heterocyclic aryl groups; preferably, ar' is methyl, ethyl, phenyl, biphenyl or naphthyl;
Figure FDA0003912651230000081
represents Ar 1 And L 1 The connecting key of (2).
5. The heterocyclic compound according to claim 1, wherein L is 1 Selected from a single bond or a group consisting of the following groups III-1 to III-23:
Figure FDA0003912651230000082
Figure FDA0003912651230000091
wherein the dotted line represents the attachment site of the group.
6. The heterocyclic compound according to any one of claims 1 to 5, characterized in that the heterocyclic compound is selected from compounds represented by the following formulae J475 to J600:
Figure FDA0003912651230000092
Figure FDA0003912651230000101
Figure FDA0003912651230000111
Figure FDA0003912651230000121
Figure FDA0003912651230000131
Figure FDA0003912651230000141
wherein, T 3 -is selected from-O-, -S-, or one of the following structures:
Figure FDA0003912651230000151
* -and-represent a bond.
7. Use of the heterocyclic compound described in any one of claims 1 to 6 for the preparation of an organic electroluminescent element.
8. An organic electroluminescent element, characterized by comprising: the organic light-emitting diode comprises a first electrode, a second electrode, a capping layer and more than one organic layer arranged between the first electrode and the second electrode; the material of at least one of the organic layer or capping layer comprises the heterocyclic compound of any one of claims 1 to 6.
9. The organic electroluminescent element according to claim 8, 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.
10. A consumer product comprising the organic electroluminescent element according to claim 8.
CN202211328091.2A 2022-10-27 2022-10-27 Heterocyclic compound and application thereof Pending CN115724826A (en)

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