CN115724826B - A heterocyclic compound and its application - Google Patents
A heterocyclic compound and its application Download PDFInfo
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Abstract
本发明涉及有机电致发光材料技术领域，尤其涉及一种杂环化合物及其应用。所述杂环化合物的结构式如式(I)所示；本发明提供的式(I)所示化合物，具有菲啶环的结构。将该化合物应用在有机电致发光元件中，可显著降低驱动电压、提高发光效率和寿命；
The present invention relates to the technical field of organic electroluminescent materials, and in particular to a heterocyclic compound and its application. The structural formula of the heterocyclic compound is shown in formula (I); the compound shown in formula (I) provided by the present invention has a phenanthridine ring structure. The compound is applied in an organic electroluminescent element to significantly reduce the driving voltage, improve the luminous efficiency and lifespan;
Description
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 that light is emitted when electric energy is applied to an organic material, that is, when an organic layer is disposed between an anode and a cathode, holes are injected from the anode to the organic layer and electrons are injected from the cathode to the organic layer if a voltage is applied between the two electrodes, excitons are formed when the injected holes and electrons meet, and light and heat are emitted when the excitons transition to a ground state.
In recent years, the organic electroluminescent display technology has tended to mature, and some products have entered the market, but in the industrialization process, many problems still remain to be solved. In particular, various organic materials used for manufacturing devices have many problems such as carrier injection and transport properties, electroluminescence properties of materials, service life, color purity, matching between various materials and between electrodes, and the like, and particularly substances applied to an electron injection layer and a transport layer, and as an earliest report on an electron transport material, typical substances for an electron transport layer including oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and imidazole groups described in CN107573328A, CN107556310A, CN113801066A, CN113429395A, CN113429348A, CN114560872a and the like, which contain N-phenylbenzimidazole groups in their structures, have not only an ability to transport electrons but also a function to block holes crossing from a light emitting layer, but have a problem of low thermal stability when applied to a practical device.
In order to overcome the above-described problems, there is a continuing need for the development of a more stable and effective substance that can be used as an electron injection and transport substance in an organic electroluminescent element, in order to further improve the characteristics of the organic electroluminescent element.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a heterocyclic compound which can improve the thermal stability of materials and the capacity of transporting carriers, an organic electroluminescent element prepared by the heterocyclic compound can obviously reduce driving voltage and improve luminous efficiency and service life, and the invention also aims to provide application of the compound.
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,
L 1 is selected from the group consisting of a single bond, a substituted or unsubstituted C 6-C60 arylene, or a substituted or unsubstituted C 2-C60 heteroarylene;
Each X 3～X6 is independently CR 2 or N;
x 1 and X 2 represent groups of the following formula (II) or formula (III);
A represents, identically or differently on each occurrence, CR 3 or N, and "≡" indicates the adjacent groups X 1 and X 2 in formula (I);
G represents O, S or NR 4;
Each R 1、R2、R3、R4 is independently selected from the group consisting of hydrogen, deuterium, fluorine, hydroxyl, nitrile, nitro, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, substituted or unsubstituted C 1-C40 alkyl, substituted or unsubstituted C 1-C40 alkoxy, substituted or unsubstituted C 2-C40 alkenyl, substituted or unsubstituted C 1-C40 alkylthio, substituted or unsubstituted C 1-C40 alkoxy, substituted or unsubstituted C 3-C40 cycloalkyl, substituted or unsubstituted C 1-C40 alkyl sulfoxide, substituted or unsubstituted C 6-C60 aryl, substituted or unsubstituted C 6-C60 aryloxy, substituted or unsubstituted C 6-C60 arylthio, substituted or unsubstituted C 6-C60 aryl sulfoxide, substituted or unsubstituted C 3-C40 silyl, substituted or unsubstituted boron, substituted or unsubstituted amino, substituted or unsubstituted aryl phosphine, substituted or unsubstituted phosphine oxide, or substituted or unsubstituted C 2-C60 heterocyclic aryl;
Ar 1 is selected from the group consisting of substituted or unsubstituted C 6-C60 aryl, substituted or unsubstituted C 6-C60 fused ring aryl, substituted or unsubstituted C 6-C60 arylamine group, or substituted or unsubstituted C 2-C60 heterocyclic aryl.
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 a phenanthridine derivative containing nitrogen is bonded to a heterocyclic ring containing formula (II) or formula (III) through arylene group or heteroarylene group L 1 to form a basic skeleton. The compound represented by the formula (I) of the present invention is electrochemically stable, has excellent electron mobility, has a high glass transition temperature, and has excellent thermal stability, as compared with the conventional phenanthridine heterocyclic structure. 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 an electron injection layer of an organic electroluminescent element. The material that can be used as any one of the light-emitting layer, the electron-transporting layer, and the electron-transporting auxiliary layer that is laminated in one step on the electron-transporting layer is preferable, and the material that can be used as the electron-transporting layer or the electron-transporting auxiliary layer is more preferable.
Specifically, the compound represented by the formula (I) of the present invention has a stronger electron transporting ability than a phenanthridine derivative having one nitrogen, which has a weak electron withdrawing group ability, by containing a phenanthridine derivative having two nitrogen, three nitrogen or four nitrogen and a heterocyclic compound having formula (II) or formula (III), and is capable of exhibiting relatively high luminous efficiency and high glass transition temperature. Thus, when the heterocyclic compound represented by the formula (I) of the present invention is used for an organic electroluminescent element, not only excellent thermal stability and carrier transport ability, particularly electron transport ability and light emitting ability, but also reduction in driving voltage of the element, improvement in efficiency, lifetime, and the like can be expected, and excellent efficiency increase due to triplet-triplet amyl fusion effect can be exhibited as a latest electron transport layer material due to high triplet energy level.
Further, the heterocyclic compound represented by the formula (I) of the present invention can have a wide band gap by introducing a plurality of substituents R 1、R2 and R 3 into a basic skeleton formed by a phenanthridine derivative containing nitrogen and a compound containing the formula (II) or the formula (III), and adjusting HOMO and LUMO energy levels according to the types of the substituents, and can exhibit the highest electron-transporting property in an organic electroluminescent element using such a compound.
In addition, the heterocyclic compound represented by the formula (I) of the present invention has a significantly increased molecular weight by introducing various substituents L 1 and Ar 1, particularly aryl and/or heteroaryl groups, into the basic skeleton, and thus has an increased glass transition temperature, thereby enabling higher thermal stability than conventional light-emitting 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.
In the heterocyclic compound of formula (I) of the present invention, X 3 to X 6 of the phenanthridine derivative containing nitrogen are the same as or different from each other, and each is independently N or CR 2. In this case, preferably, the heterocyclic compound is selected from the group consisting of:
Wherein each R 1、R2、R3 is independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, methyl, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, carbazolyl, fluorenyl, dibenzofuran, or dibenzothiophene.
Preferably, each R 1、R2、R3 is independently hydrogen or phenyl.
Preferably, G is O or S.
Preferably, ar 1 is selected from the group consisting of phenyl, naphthyl, anthracenyl, benzanthracenyl, 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, azadibenzo [ g., ij ] naphtho [2,1,8-cde ] azulene, trimeric indenyl, heterotrimeric indenyl, spirotrimeric indenyl, spiroheterotrimeric indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, 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, naphthazolyl phenanthroimidazolyl, pyridmethylimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthracooxazolyl, 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-tetrazoleperyl, pyrazinyl, and the like, 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.
In the heterocyclic compound of formula (I) of the present invention, ar 1 may be selected from the group consisting of commonly known electron withdrawing groups. In this case, ar 1 is preferably selected from the group consisting of the groups represented by the following groups II-1 to II-17:
Wherein,
Each Z 1、Z2 is independently selected from the group consisting of hydrogen, deuterium, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazino, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1-C40 alkyl, C 2-C40 alkenyl, C 2-C40 alkynyl, C 1-C40 alkoxy, C 3-C40 naphthenyl, C 3-C40 cycloalkenyl, substituted or unsubstituted C 6-C60 aryl, substituted or unsubstituted C 6-C60 aryloxy, substituted or unsubstituted C 6-C60 arylthio, substituted or unsubstituted C 6-C60 arylamino, or substituted or unsubstituted C 2-C60 heteroaryl;
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, and x5 represents an integer of 1 to 5;
T 1 represents O, S, CR 'R" or NAr ';
R '、R" are each independently selected from the group consisting of hydrogen, deuterium, alkyl of C 1～C40, heteroalkyl of C 1～C40, substituted or unsubstituted C 6-C60 aryl, substituted or unsubstituted C 6-C60 arylamine, or substituted or unsubstituted C 2-C60 heterocycloaryl, R ' and R " may optionally be joined or fused to form another one or more substituted or unsubstituted rings with or without one or more heteroatoms N, P, B, O or S in the ring formed;
Ar ' is selected from the group consisting of C 1～C40 alkyl, C 1～C40 heteroalkyl, C 3～C40 cycloalkyl, substituted or unsubstituted C 6-C60 aryl, substituted or unsubstituted C 6-C60 fused ring aryl, substituted or unsubstituted C 6-C60 arylamine, or substituted or unsubstituted C 2-C60 heteroaryl, preferably Ar ' is methyl, ethyl, phenyl, biphenyl, or naphthyl;
Ar 1 is a bond to L 1, and the groups represented by the above formulas II-1 to II-17 may each be independently substituted with one or more selected from the group consisting of deuterium, halogen atom, nitrile group, nitro group, C 1-C40 alkyl group, C 2-C40 alkenyl group, C 2-C40 alkynyl group, C 3-C40 cycloalkyl group, C 3-C40 heterocycloalkyl group, C 6-C60 aryl group and C 2-C60 heteroaryl group, C 1-C40 alkoxy group, C 6-C60 aryloxy group, C 1-C40 alkylsilyl group, C 6-C60 arylsilyl group, C 1-C40 alkylboron group, C 6-C60 arylboron group, C 6-C60 arylphosphine group, C 1-C60 arylphosphine oxide group and arylamino group of C 6-C60, and in this case, when the substituents are plural, it is preferable that the plural substituents are the same or different from each other.
In the heterocyclic compound of formula (I) of the present invention, L 1 is a functional group connecting the nitrogen-containing phenanthridine derivative to Ar 1, and may be selected from the group consisting of C 6-C60 arylene and C 2-C60 heteroarylene. In this case, preferably, the L 1 is selected from a single bond or a group consisting of the following groups III-1 to III-23:
Wherein the dotted line represents the linking site of the group, and the binding position of the group represented by the above formulas III-1 to III-23 is not limited, and may be ortho, meta or para. The above-mentioned L 1 may each independently be substituted with one or more selected from the group consisting of deuterium, a halogen atom, a nitrile group, a C 1-C40 alkyl group, a C 6-C60 aryl group and a C 2-C60 heterocyclic aryl group, and in this case, when the substituents are plural, it is preferable that the plural substituents are the same as or different from each other.
In the present invention, the term "substituted or unsubstituted" means that the compound is substituted or unsubstituted with 1 or more substituents selected from 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, a C 1-C40 alkyl group, a C 2-C40 alkenyl group, a C 2-C40 alkynyl group, a C 1-C40 alkoxy group, a C 3-C40 cycloalkyl group, a C 3-C40 cycloalkenyl group, a C 6-C60 aryl group, a C 6-C60 aryloxy group, a C 6-C60 arylene sulfide group, and a C 2-C60 heteroaryl group, or a substituent bonded with 2 or more substituents selected from the above-exemplified substituents.
Aryl groups in the sense of the present invention contain 6 to 60 carbon atoms and 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, said heteroatom preferably being 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, polycyclic rings such as phenoxathianyl, indolizinyl, indolyl, purinyl, quinolinyl, benzothiazolyl, carbazolyl, and 2-furyl, N-imidazolyl, 2-isoxazolyl, 2-pyridyl, 2-pyrimidinyl, and the like can be given.
Alkyl having 1 to 40 carbon atoms and in which the individual hydrogen atoms or-CH 2 -groups may also be substituted or branched alkyl, alkenyl or alkynyl having at least two carbon atoms is preferably understood to mean, as non-limiting examples, 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 having 1 to 40 carbon atoms 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 groups preferably having 1 to 40 carbon atoms are groups in which the individual hydrogen atoms or-CH 2 -groups are replaced by 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 -groups may be replaced by the above groups, and furthermore one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms or nitrile groups.
The heterocycloalkyl group used in the present invention means a monovalent functional group obtained by removing one hydrogen atom from a non-aromatic hydrocarbon having a atomic number of 3 to 40. At this time, one or more carbons, preferably 1 to 3 carbons, in the ring are substituted with a heteroatom such as N, O or S. As non-limiting examples thereof, tetrahydrofuran, tetrahydrothiophene, morpholine, piperazine, and the like are given.
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 herein refers to a monovalent functional group represented by RO -, where R is an alkyl group having 1 to 40 carbon atoms and may comprise 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.
The aryloxy group used in the present invention means a monovalent functional group represented by R 'O -, and R' is an aryl group having 6 to 60 carbon atoms. As non-limiting examples of such aryloxy groups, there are phenoxy, naphthoxy, biphenyloxy, and the like.
The alkylsilyl group used in the present invention means a silyl group substituted with an alkyl group having 1 to 40 carbon atoms, and the number of carbon atoms constituting the alkylsilyl group is at least 3, and as non-limiting examples of the alkylsilyl group, there are trimethylsilyl group, triethylsilyl group and the like. Arylsilyl refers to silyl groups substituted with aryl groups having from 6 to 60 carbon atoms.
The arylphosphorus group used in the present invention means a diarylphosphorus group substituted with an aryl group having 6 to 60 carbon atoms, and as non-limiting examples of the arylphosphorus group, there are diphenylphosphorus group, bis (4-trimethylsilylbenzene) phosphorus group and the like. The phosphorus atom of the aryl phosphorus oxide group is the diaryl phosphorus group is oxidized to the highest valence state.
The arylboron group used in the present invention means a diarylboroyl group substituted with an aryl group having 6 to 60 carbon atoms, and as non-limiting examples of the arylboron group, there are diphenyl boron group, bis (2, 4, 6-trimethylbenzene) boron group and the like. The alkylboryl group means a dialkylboryl group substituted with an alkyl group having 1 to 40 carbon atoms, and as non-limiting examples of the alkylboryl group, there are di-t-butylboryl group, diisobutylboryl group and the like.
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, azadibenzo [ g., ij ] naphtho [2,1,8-cde ] azulene, trimeric indenyl, heterotrimeric indenyl, spirotrimeric indenyl, spiroheterotrimeric indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, 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, naphthazolyl phenanthroimidazolyl, pyridmethylimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthracooxazolyl, 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-tetrazoleperyl, pyrazinyl, and the like, 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.
Preferably, the heterocyclic compound is selected from the group consisting of compounds represented by the following formulas J475-J600:
Wherein,
* -T 3 - (O-) is selected from one of the following structures:
* -and- (x) represents a bond.
The invention also provides a preparation method of the heterocyclic compound, which is shown in scheme 1:
In the case of scheme 1, the method comprises,
In scheme 1, the symbols used are as defined in formula (I) and Y is Cl, br, I or OTf;
The raw materials for synthesizing the compound shown in the formula (I) can be purchased through commercial paths, and the method principles, the operation process, the conventional post-treatment, the column purification, the recrystallization purification and other means are well known to the synthesis personnel in the field, so that the synthesis process can be completely realized to obtain the target product.
Specifically, the compound of the formula (I) is prepared by performing coupling substitution reaction on o-nitrile halogenated S0 and alkyne to prepare an intermediate S1, preparing an intermediate S2 by closing a ring with nitromethane, preparing an o-nitro halogenated intermediate S3 by performing diazotization substitution reaction on the intermediate S1 and the S2 with amino, preparing a compound S4 by performing SUZUKI coupling reaction on the intermediate S3 and boric acid or pinacol borate of o-R 1 formyl, and preparing the compound of the formula (I) by performing condensation reaction on carbonyl and nitro of the compound S4. Intermediate Ar 1-L1 -Y and alkyne derivatives thereof are prepared by palladium catalysis or base catalysis coupling reaction.
The palladium catalyst which can be used for the palladium-catalyzed coupling reaction may be any one selected from ：Pd(P-tBu3)2、Pd(PPh3)4、Pd2(dba)3、Pd2(dba)3CHCl3、PdCl2(PPh3)2、PdCl2(CH3CN)2、Pd(OAc)2、Pd(acac)2、Pd/C、PdCl2、[Pd(allyl)Cl]2 and the like, or a mixture of two or more kinds may be used.
In addition, the base used for the palladium-catalyzed coupling reaction or the base-catalyzed coupling reaction may be selected from sodium t-butoxide, potassium t-butoxide, sodium hydride, lithium hydride, sodium t-amyl alcohol, sodium ethoxide, sodium methoxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium, potassium hydride, triethylamine, cesium fluoride, and the like, and a mixture of one or two or more thereof.
The coupling reaction may be carried out in an organic solvent selected from ether solvents such as diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, ethylene glycol diethyl ether, ethylene glycol methyl ether, diethylene glycol diethyl ether, anisole, aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, etc., and a mixture of one or more of them may be used.
The invention also provides an organic electroluminescent material, which comprises the heterocyclic compound, wherein the organic electroluminescent material comprising the heterocyclic compound has the carrier transmission capability.
The invention also provides application of the heterocyclic compound in preparation of an organic electroluminescent element.
The invention also provides an organic electroluminescent element, which comprises a first electrode, a second electrode, a sealing layer and more than one organic layer arranged between the first electrode and the second electrode, wherein at least one layer of the organic layer or the sealing layer comprises the heterocyclic compound.
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. The person skilled in the art will thus be able to use all materials known for organic electroluminescent elements in combination with the luminescent 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 material is applied by vapor deposition in a vacuum sublimation apparatus at an initial pressure of less than 10 -5 Pa, preferably less than 10 -6 Pa. However, the initial pressure may also be even lower, for example below 10 -7 Pa.
Also preferred are organic electroluminescent elements in which one or more layers are applied by means of an organic vapor deposition process or by means of sublimation of a carrier gas, wherein the material is applied at a pressure of between 10 -5 Pa and 1 Pa. A particular example of this method is an organic vapor jet printing method, wherein the material is applied directly through a nozzle and is thus structured.
Furthermore, organic electroluminescent elements are preferred, from which one or more layers are produced, for example by spin coating, or by means of any desired printing method, for example screen printing, flexography, lithography, photoinitiated thermal imaging, thermal transfer, inkjet printing or nozzle printing. Soluble compounds, for example, are obtained by appropriate substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, a hybrid method is possible, in which one or more layers are applied, for example from a solution, and one or more further layers are applied by vapor deposition.
These methods are generally known to those of ordinary skill in the art and they can be applied to the organic electroluminescent element comprising the compound according to the present invention without inventive effort.
The invention therefore also relates to a method for manufacturing an organic electroluminescent element according to the invention, at least one layer being applied by means of a sublimation method, and/or characterized in that at least one layer is applied by means of an organic vapour deposition method or by means of carrier gas sublimation, and/or in that at least one layer is applied from solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to heterocyclic compounds comprising at least one of the above-indicated invention. The same preferable cases as indicated above with respect to the organic electroluminescent element apply to the compound of the present invention. In particular, it may be preferable to contain other compounds in addition to the heterocyclic compound. Treatment of the heterocyclic compounds of the present invention from the liquid phase, for example by spin coating or by printing methods, requires treatment of the formulations of the compounds of the present invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchyl ketone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylbenzene, 3, 5-dimethylbenzene, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1-bis (3, 4-dimethylphenyl) ethane, or mixtures of these solvents.
Preferably, the organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, or an electron blocking layer.
The invention also provides a consumer product comprising the organic electroluminescent element.
In addition, unless otherwise specified, all raw materials used in the present invention are commercially available, and any ranges recited in the present invention include any numerical value between the end values and any sub-range constituted by any numerical value between the end values or any numerical value between the end values.
The beneficial effects obtained by the invention are as follows:
the heterocyclic compound represented by formula (I) provided by the invention can be applied to an organic layer of an organic electroluminescent element due to excellent electron mobility, thermal stability and luminescence characteristics. In particular, when the heterocyclic compound represented by the formula (I) of the present invention is used for an electron transport layer and an electron transport auxiliary layer, an organic electroluminescent element having a lower driving voltage, higher efficiency and longer lifetime than conventional electron transport materials can be produced, and further, a full-color display panel having improved performance and lifetime can be produced.
Drawings
Fig. 1 shows a schematic diagram of an organic light emitting device 100. The illustrations are not necessarily drawn to scale. The device 100 may include a substrate 101, an anode 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 layers described.
Fig. 2 shows a schematic diagram of an organic light emitting device 200 with two light emitting layers. The device includes a substrate 201, an anode layer 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 layer 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 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 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, and the orientation or positional relationship indicated by the terms "upper", "lower", etc. are based on the orientation or positional relationship shown in the drawings, merely to facilitate description of the present invention and to simplify the description, and are not indicative of or implying that the apparatus or element being referred to must have a particular orientation, be constructed and operated in a particular 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 were measured using spectral scanners PhotoResearch PR-715;
current density and lighting voltage were tested using the digital source table Keithley 2420;
power efficiency-using NEWPORT 1931-C test.
Example 1
A process for preparing compound J475 comprising the steps of:
First step, preparation of intermediate Int-1
Under the protection of nitrogen, 20.0mmol of o-iodobenzonitrile is dissolved in 60mL of triethylamine, 22.0mmol of p-chloroacetylene, 2.0mmol of cuprous iodide and 0.2mmol of PdCl 2(PPh3)2 catalyst are added for reaction for 12 hours under stirring, the filtrate is filtered, reduced pressure concentration is carried out on the filtrate, and separation and purification are carried out on the filtrate by a silica gel column to obtain an intermediate Int-1 with the yield of 93%.
Second step, preparing intermediate Int-2
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 ℃, stirring reaction is carried out for 1 hour, the temperature is reduced to room temperature, 150mL of saturated sodium bisulphite aqueous solution is added, extraction is carried out by ethyl acetate, an organic phase is dried, filtered, concentrated and dried under reduced pressure, and separation and purification are carried out by an alumina column, thus obtaining orange solid with the yield of 86 percent.
Third step, preparing intermediate Int-3
Under the protection of nitrogen, 20.0mmol of Int-2 is dissolved in 50mL of acetonitrile, 40mL of 48% hydrobromic acid and 40mL of water are added, ice bath is cooled to 0 ℃, 24.0mmol of sodium nitrite solution dissolved in water is slowly added dropwise, stirring reaction is carried out for 1 hour, 24.0mmol of cuprous bromide is added in portions, the temperature is raised to room temperature, stirring reaction is carried out for 2 hours, extraction is carried out by ethyl acetate, an organic phase is washed by saturated brine, the organic phase is collected and dried, filtration and reduced pressure concentration are carried out on the filtrate, and yellow solid Int-3 is obtained through separation and purification by a silica gel column, wherein the yield is 73%.
Fourth, the intermediate Int-4 is prepared
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, then 0.01mmol of Pd132 catalyst, 20mL of ethanol and 20mL of water are added, the mixture is heated to reflux and stirred for reaction for 12 hours, cooled to room temperature, 50mL of water is added for dilution, dichloromethane is used for extraction, an organic phase is collected, dried, filtered, the filtrate is concentrated under reduced pressure, and the compound Int-4 is obtained by separation and purification by a silica gel column, and yellow solid is obtained with the yield of 76%.
Fifth step, preparation of intermediate A1
Under the protection of nitrogen, 20.0mmol of Int-4 is mixed with 50mL of glacial acetic acid, the temperature is raised to 100 ℃, 60.0mmol of iron powder is added in batches, the temperature is raised to reflux and stirring for reaction for 2 hours, the temperature is reduced, the filtration is carried out, the filtrate is concentrated under reduced pressure, 100mL of ethyl acetate is added for dissolution, the water is washed, the organic phase is dried, the filtration is carried out, the filtrate is concentrated under reduced pressure, and the compound A1, pale yellow solid and the yield 82% are obtained through separation and purification by a silica gel column.
Referring to the above-described analogous synthetic methods, the following compounds were prepared:
sixth, intermediate Int-6 is prepared
Under the protection of nitrogen, 20.0mmol of A1 is dissolved in 60mL of dry DMF, 24.0mmol of pinacol biborate, 30.0mmol of anhydrous potassium acetate, 0.2mmol of PdCl 2 (dppf) and 2.0mmol of cuprous iodide are added, the temperature is raised to 100 ℃, the reaction is stirred for 12 hours and cooled to room temperature, the reaction solution is poured into 120mL of water, the water is filtered, the filter cake is washed with water, dried, and then silica gel column separation and purification are carried out to obtain white solid with the yield of 78 percent.
Seventh step, preparation of Compound J475
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, then 0.01mmol of Pd132 catalyst, 20mL of ethanol and 20mL of water are added, the mixture is heated to reflux and stirred for reaction for 12 hours, cooled to room temperature, 50mL of water is added for dilution, dichloromethane is used for extraction, an organic phase is collected, dried, filtered, the filtrate is concentrated to dryness under reduced pressure, and the compound J475, white solid and the yield are obtained by separating and purifying the compound by a silica gel column 76％,MS(MALDI-TOF)：m/z＝537.2095[M+H]+;1HNMR(δ、CDCl3)：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).
Referring to the above synthetic method, the following compounds shown in table 1 were prepared:
TABLE 1
Example 2
A process for the preparation of compound J552 comprising the steps of:
First step, preparation of intermediate Int-7
Referring to the synthesis of the first step of example 1, the substitution of SM-1 for SM-2 and p-chloroacetylene for o-chloroacetylene in the first step of example 1 produced intermediate Int-7 in 87% yield.
Second step, preparing intermediate Int-8
Referring to the synthesis of the second step of example 1, the substitution of Int-1 in the second step of example 1 with Int-7 produced intermediate Int-8 in 87% yield.
Third step, preparing intermediate Int-9
Referring to the synthesis method of the third step of example 1, the intermediate Int-9 was prepared in 75% yield by substituting Int-2 in the third step of example 1 with Int-8.
Fourth, the intermediate Int-10 is prepared
Referring to the synthesis method of the fourth step of example 1, only Int-3 in the fourth step of example 1 was replaced with Int-9 to prepare intermediate Int-10 in a yield of 74%.
Fifth step, preparing intermediate Int-11
Referring to the synthesis method of the fifth step of example 1, only Int-4 in the fifth step of example 1 was replaced with Int-10 to prepare intermediate Int-11 in a yield of 81%.
Sixth step preparation of Compound J552
Under the protection of nitrogen, 12.0mmol of intermediate Int-11, 10.0mmol of 15H-azepine [2,3,4,5-def:6,7,1-J 'k' ] dicarbazole, 15.0mmol of tertiary sodium butoxide, 0.01mmol of Pd 2(dba)3 catalyst, 0.04mmol of 10% tri-tertiary butyl phosphine toluene solution and 50mL of xylene are reacted for 12 hours under stirring at the temperature of 110 ℃, cooled to room temperature, diluted with 50mL of water, extracted with dichloromethane, the organic phase is collected, dried, filtered, and the filtrate is concentrated under reduced pressure, and separated and purified by a silica gel column to obtain a compound J552 as a yellow solid, and the yield is improved 78％,MS(MALDI-TOF)：m/z＝636.2206[M+H]+;1HNMR(δ、CDCl3)：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).
Referring to the above-described similar synthetic method, the following compounds shown in table 2 were prepared:
TABLE 2
In the above-described embodiments, the first and second embodiments, -T 3 - (O) -is selected from one of the following structures:
* -and- (x) represents a bond.
Example 3
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 layer 110 disposed on the electron injection layer 109 and a capping layer 111 disposed on the cathode layer, wherein the method for preparing the OLED element not including 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 a vacuum chamber, vacuumizing to less than 1× -5 Pa, evaporating metallic silver as anode layer on the ITO film, and evaporating film thickness to beContinuing to vapor deposit the compounds HI01 and F4TCNQ respectively as hole injection layers, 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 compound shown in the formula (I) is used as a main material and RD11 is used as a doping material, RD11 is 3 percent of the mass of the compound shown in the formula (I) and is used as an organic light-emitting layer of the element, and the film thickness of the organic light-emitting layer obtained by evaporation plating is
6) Continuously evaporating an electron transport layer with LiQ and a compound ET025 as elements on the organic light-emitting layer, wherein the compound ET025 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 1:10, 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 3 above is as follows:
Example 4
An organic electroluminescent device 200, the structure of which is shown in fig. 2, comprises a substrate 201, an anode layer 202, a hole injection layer 203, a hole transport layer 204, a first luminescent layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second luminescent layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode layer 213.
Comparative example 1
By following the same procedure as in example 3, substituting the compound of formula (I) in step 5) with H01, comparative element 1 was obtained;
Comparative example 2
By following the same procedure as in example 3, substituting the compound of formula (I) in step 5) with H02, comparative element 2 was obtained;
Comparative example 3
By following the same procedure as in example 3, substituting the compound of formula (I) in step 5) with H03, comparative element 3 is obtained;
Comparative example 4
By following the same procedure as in example 3, substituting the compound of formula (I) in step 5) with H04, comparative element 4 was obtained;
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 3 and 4 and comparative examples 1 to 4 were measured using a digital source meter and a luminance meter. Specifically, the voltage was increased at a rate of 0.1V per second, the driving voltage, which is the voltage when the luminance of the organic electroluminescent element reached 1000cd/m 2, was measured, and the current density at this time was measured, and the ratio of the luminance to the current density, which is the current efficiency, was measured, and the LT95% lifetime test was as follows, the time, in hours, in which the luminance decay of the organic electroluminescent element was 950cd/m 2, was measured using a luminance meter at a luminance of 1000cd/m 2. The data listed in table 3 are relative data compared to comparative element 1.
TABLE 3 Table 3
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 than H01 under the same brightness, a significantly improved current efficiency up to as much as 1.3 times that of the comparative device, and a significantly improved LT95% lifetime of the device.
The compound H01 in comparative example 1 is different from the compound of the present invention in that the phenanthridine nitrogen ortho-position introduces a substituent group and then the plane conjugation ability is weak, resulting in high voltage and lower efficiency. The compound of the invention has strong conjugation capability of introducing substituent groups on benzene rings, has more excellent performance on molecular film formation and charge transmission, and more balanced charge transmission in elements, thus the element performance is obviously improved.
The compound H02 of comparative example 2 is different from the compound of the present invention in that phenanthridine incorporates a phenyl group, and the planar conjugation ability is enhanced, but the steric hindrance is increased, the molecular film formation and charge transport properties are lowered, resulting in high voltage and reduced efficiency. The compound of the invention increases the conjugation plane and reduces the steric hindrance, so that the compound has more excellent performance in molecular film formation and charge transmission, and more balanced charge transmission in the element, thereby obviously improving the element performance.
The compound H03 of comparative example 3 is different from the compound of the present invention in that phenanthridine incorporates a phenyl group and a phenyl group is introduced in the ortho-position to nitrogen, and although the planar conjugation ability is enhanced, the steric hindrance is increased, the molecular film formation and charge transport properties are lowered, resulting in high voltage and reduced efficiency. The compound of the invention introduces substituent groups on the same side of nitrogen, but does not introduce ortho-position of nitrogen, increases conjugate plane, and reduces steric hindrance, so that the compound has more excellent performance in molecular film formation and charge transmission, and more balanced charge transmission in the element, thus obviously improving the element performance.
The compound H04 in comparative example 4 is different from the compound of the present invention in that two electron withdrawing groups are introduced based on benzophenanthridine, the planar conjugation ability is lowered, the molecular film forming and charge transporting properties are lowered, resulting in high voltage and reduced efficiency. The compound of the invention introduces electron withdrawing group or strong electron donating group at the same time of increasing the conjugation plane of the mother nucleus and at the same side of nitrogen instead of ortho position to improve the electron transmission performance, therefore, the compound has more excellent performance in molecular film formation and charge transmission, and the charge transmission in the element is more balanced, thus the element performance is obviously improved.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (4)
1. A heterocyclic compound selected from the group consisting of compounds represented by formulas J475-J600:
wherein-T 3 -is selected from-O-, S-, or one of the structures shown below:
* -and- (x) represents a bond.
2. Use of the heterocyclic compound according to claim 1 for producing an organic electroluminescent element.
3. 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, wherein at least one of the organic layers or the capping layer comprises the heterocyclic compound according to claim 1.
4. The organic electroluminescent element according to claim 3, 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.
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| CN103382178A (en) * | 2012-05-03 | 2013-11-06 | 三星显示有限公司 | Condensed-cyclic compound and organic light-emitting diode comprising the same |
| CN103804333A (en) * | 2012-11-01 | 2014-05-21 | 三星显示有限公司 | Heterocyclic compound and organic light emitting diode comprising the same |
| CN105358533A (en) * | 2013-12-27 | 2016-02-24 | 喜星素材株式会社 | Heterocyclic compound and organic light emitting device using same |
| KR20160007438A (en) * | 2014-07-11 | 2016-01-20 | 희성소재 (주) | Hetero-cyclic compound and organic light emitting device using the same |
| KR20160082067A (en) * | 2014-12-30 | 2016-07-08 | 희성소재 (주) | Compound and organic light emitting device using the same |
| CN105859776A (en) * | 2015-02-05 | 2016-08-17 | 三星显示有限公司 | Compound and organic light emitting device comprising same |
| KR20160107669A (en) * | 2015-03-05 | 2016-09-19 | 에스에프씨 주식회사 | Novel organic light-emitting diode including antracene derivatives |
| KR20180010409A (en) * | 2016-07-21 | 2018-01-31 | 에스에프씨 주식회사 | Novel anthracene derivatives and organic light-emitting diode therewith |
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| CN115724826A (en) | 2023-03-03 |
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