CN116023275A - Triamine derivative and organic light-emitting device thereof - Google Patents
Triamine derivative and organic light-emitting device thereof Download PDFInfo
- Publication number
- CN116023275A CN116023275A CN202310125475.2A CN202310125475A CN116023275A CN 116023275 A CN116023275 A CN 116023275A CN 202310125475 A CN202310125475 A CN 202310125475A CN 116023275 A CN116023275 A CN 116023275A
- Authority
- CN
- China
- Prior art keywords
- substituted
- unsubstituted
- group
- butyl
- ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a triamine derivative and an organic light-emitting device thereof, and relates to the technical field of organic photoelectric materials. The problems of low luminous efficiency, short service life and the like of most of the current organic light-emitting devices are mainly solved. The derivative takes benzene as a center, and at least one or two alkyl groups are connected to the center benzene, so that the derivative has good film forming property and thermal stability. On the other hand, the material has good hole mobility and proper HOMO energy level and T1 value, and can effectively improve the luminous efficiency of the device and prolong the service life of the device when being applied to an organic luminous device as a hole transport layer material. The derivative disclosed by the invention is combined with the heterocyclic compound shown in the formula II to be applied to a device, so that the maximum recombination of carriers is realized, and the luminous efficiency and the service life of the device are improved. The organic light source can be widely applied to the fields of panel display, illumination light sources, organic solar cells, organic photoreceptors or organic thin film transistors and the like.
Description
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a triamine derivative and an organic light-emitting device thereof.
Background
Along with the development of electronic technology and the progress of material science, the application range of electronic components for realizing electroluminescence or photoelectric conversion is becoming wider and wider. Organic light emitting devices (OLED: organic electroluminescent device) are a new generation of display technology, and have the characteristics of self-luminescence, wide viewing angle, short reaction time, high luminous efficiency, wide color gamut, etc., so as to gradually enter the field of view of people.
The organic light emitting device includes an anode on a substrate, and an organic layer and a cathode of a hole transport region, an emission layer, an electron transport region, and a capping layer outside the cathode are sequentially formed on the anode. The organic light emitting device further combines positive and negative charges in the organic layer under the driving of an electric field by applying a voltage across the electrodes, that is, the electrons and holes are combined in the light emitting layer to generate light emission, so it is important to improve the recombination of electrons and holes in the OLED device.
In the present stage, the types of hole transport and electron transport materials applied to the organic light emitting device are limited, so that the organic light emitting device still has a plurality of problems to be solved, the materials commonly used for the hole transport layer at present have the problems of low hole mobility, low glass transition temperature and the like, electrons and hole transport cannot reach balance, excitons cannot be effectively combined, and at the same time, triplet energy level is low, so that the loss of excitons to the hole transport layer cannot be effectively avoided, and the light emitting efficiency of the device is low and the stability of the device is reduced.
In order to solve the above problems, a hole transport material having high hole mobility, high glass transition temperature, high triplet energy level and good moldability has been studied.
Disclosure of Invention
The invention aims to provide a triamine derivative and an organic light-emitting device thereof based on the prior art and aiming at industrialization, and provides the triamine derivative, wherein the molecular structural general formula of the triamine derivative is shown as formula I:
wherein the R is 1 、R 2 At least one of which is selected from substituted or unsubstituted C1-C10 alkyl, R 3 A substituent selected from hydrogen, cyano or halogen, and the substituent in the 'substituted or unsubstituted' is selected from one or more of methyl, ethyl, isopropyl and tert-butyl;
the Ar is as follows 1 A substituted or unsubstituted aryl group of 10 to 25 carbon atoms, wherein the substituent in the "substituted or unsubstituted" group is selected from one or more of cyano, halogen, methyl, ethyl, isopropyl and tert-butyl;
the Ar is as follows 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from the group represented by formula a:
the R is m The same or different R is selected from one of hydrogen, cyano, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, or two adjacent R m The groups may be bonded to form a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring, wherein the substituents in "substituted or unsubstituted" are selected from one or more of cyano, halogen, methyl, ethyl, isopropyl, tert-butyl;
the m is 1 Selected from 0, 1, 2, 3, 4 or 5;
the L is 1 、L 2 、L 3 、L 4 、L 5 、L 6 Independently selectOne of single bond, substituted or unsubstituted C6-C25 arylene, wherein the substituent in the "substituted or unsubstituted" is selected from one or more of cyano, halogen, methyl, ethyl, isopropyl and tert-butyl.
The invention also provides an organic light-emitting device, which comprises an anode, a cathode and an organic layer, wherein the organic layer is positioned between the anode and the cathode or outside one or more than one of the anode and the cathode, and the organic layer contains any one or a combination of at least two of the triamine derivatives.
The invention has the beneficial effects that:
the invention provides a triamine derivative and an organic light-emitting device thereof, which take benzene as a center, are connected with three triarylamines, and are at least connected with one or two alkyl groups (straight chain or branched chain) on the center benzene. On the other hand, the derivative has good hole mobility, proper HOMO energy level and T1 value, and can effectively improve the luminous efficiency of the device and prolong the service life of the device when being applied to an organic luminous device, especially when being used as a hole transport layer material.
The triamine derivative shown in the formula I is applied to a hole transmission layer, the heterocyclic compound shown in the formula II is applied to an electron transmission region, and the triamine derivative and the heterocyclic compound are combined and applied to an organic light-emitting device, so that the transmission efficiency of holes and electrons in the device is improved, the holes and electrons are effectively blocked in the light-emitting layer, the maximum recombination of carriers is realized, and the light-emitting efficiency and the service life of the organic light-emitting device are improved.
Detailed Description
The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is shown, however, only some, but not all embodiments of the invention are shown. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.
In the compounds of the present invention, any atom not designated as a particular isotope is included as any stable isotope of that atom, and includes atoms in both its natural isotopic abundance and non-natural abundance. Taking hydrogen as an example, each hydrogen atom of all naturally occurring compounds contains about 0.0156 atomic% deuterium.
In the present invention, the use of "H" and "hydrogen" means that the hydrogen atoms in the chemical structure contain no more than the natural abundance of deuterium or tritium atoms, for example, no more than 0.0156 atomic% deuterium. "D" and "deuterium" refer to any value where the abundance of deuterium content is above natural abundance, e.g., above 0.1 atomic%, above 1 atomic%, above 10 atomic%, e.g., where about 95 atomic% is deuterium. "T" and "tritium" refer to any value where the abundance of tritium content is above natural abundance, e.g., greater than 0.1 atomic%, greater than 1 atomic%, greater than 10 atomic%, e.g., where about 95% is tritium. In the present invention, the omitted hydrogen atom represents "H" or "hydrogen".
In this specification, when the position of a substituent on an aromatic ring is not fixed, it means that it can be attached to any of the corresponding optional positions of the aromatic ring. For example, the number of the cells to be processed,
can indicate->
And so on.
Halogen in the present invention means fluorine, chlorine, bromine and iodine.
The alkyl group according to the present invention is a hydrocarbon group having at least one hydrogen atom in the alkane molecule, and may be a straight chain alkyl group or a branched chain alkyl group, and preferably has 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The straight-chain alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl and the like; the branched alkyl group includes, but is not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, an isomeric group of n-pentyl, an isomeric group of n-hexyl, an isomeric group of n-heptyl, an isomeric group of n-octyl, an isomeric group of n-nonyl, an isomeric group of n-decyl, and the like. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.
The chain alkyl group having more than three carbon atoms according to the present invention includes isomers thereof, for example, propyl group includes n-propyl group, isopropyl group, butyl group includes n-butyl group, sec-butyl group, isobutyl group, tert-butyl group. And so on.
Cycloalkyl as used herein refers to a hydrocarbon group having at least one hydrogen atom in the cycloparaffin molecule, preferably having 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, particularly preferably 3 to 6 carbon atoms, and examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, camphene, norbornyl, etc., but are not limited thereto. The cycloalkyl group is preferably cyclobutyl, cyclopentyl or cyclohexyl.
The heterocycloalkyl group refers to a monovalent group in which at least one parent carbon atom in the heterocycloalkyl group is replaced with a heteroatom. Such heteroatoms include, but are not limited to, atoms as described below, N, O, S, si, B, P, and the like. Preferably having 3 to 30 carbon atoms, more preferably 3 to 15 carbon atoms, still more preferably 3 to 10 carbon atoms. Examples of heterocycloalkyl groups include, but are not limited to, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, homopiperidinyl, morpholinyl, thiomorpholinyl, piperazinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, and the like.
Aryl in the present invention refers to the generic term for monovalent radicals remaining after removal of one hydrogen atom from the aromatic nucleus carbon of an aromatic compound molecule, which may be a monocyclic aryl, polycyclic aryl or fused ring aryl, preferably having from 6 to 25 carbon atoms, more preferably from 6 to 20 carbon atoms, particularly preferably from 6 to 14 carbon atoms, and most preferably from 6 to 12 carbon atoms. The monocyclic aryl refers to aryl having only one aromatic ring in the molecule, for example, phenyl, etc., but is not limited thereto; the polycyclic aryl group refers to an aryl group having two or more independent aromatic rings in the molecule, for example, biphenyl, terphenyl, etc., but is not limited thereto; the condensed ring aryl group refers to an aryl group having two or more aromatic rings in the molecule and condensed by sharing two adjacent carbon atoms with each other, for example, but not limited to, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylenyl, fluoranthryl, spirobifluorenyl, and the like. The aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group (preferably a 2-naphthyl group), an anthryl group (preferably a 2-anthryl group), a phenanthryl group, a pyrenyl group, a perylenyl group, a fluorenyl group, a benzofluorenyl group, a triphenylenyl group, or a spirobifluorenyl group.
Heteroaryl according to the present invention refers to the generic term for groups in which one or more aromatic nucleus carbon atoms in the aryl group are replaced by heteroatoms, including but not limited to oxygen, sulfur, nitrogen or phosphorus atoms, preferably having 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, most preferably 3 to 12 carbon atoms, the attachment site of the heteroaryl group may be located on a ring-forming carbon atom, or on a ring-forming nitrogen atom, and the heteroaryl group may be a monocyclic heteroaryl, polycyclic heteroaryl or fused ring heteroaryl. The monocyclic heteroaryl group includes, but is not limited to, pyridyl, pyrimidinyl, triazinyl, furyl, thienyl, pyrrolyl, imidazolyl, and the like; the polycyclic heteroaryl group includes bipyridyl, bipyrimidinyl, phenylpyridyl, etc., but is not limited thereto; the fused ring heteroaryl group includes, but is not limited to, quinolinyl, isoquinolinyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothiophenyl, benzodibenzothiophenyl, carbazolyl, benzocarbazolyl, acridinyl, 9, 10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiazinyl, and the like. The heteroaryl group is preferably a pyridyl group, a pyrimidyl group, a thienyl group, a furyl group, a benzothienyl group, a benzofuryl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a dibenzofuryl group, a dibenzothienyl group, a benzodibenzothienyl group, a benzodibenzofuryl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group, or a phenoxathiazide group.
The arylene group according to the present invention means a generic term for divalent groups remaining after removal of two hydrogen atoms from the aromatic nucleus carbon of an aromatic compound molecule, which may be a monocyclic arylene group, a polycyclic arylene group or a condensed ring arylene group, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic arylene group includes phenylene and the like, but is not limited thereto; the polycyclic arylene group includes biphenylene, terphenylene, etc., but is not limited thereto; the condensed ring arylene includes, but is not limited to, naphthylene, anthrylene, phenanthrylene, fluorenylene, pyreylene, triphenylene, fluoranthenylene, phenylenedenyl, and the like. The arylene group is preferably phenylene, biphenylene, terphenylene, naphthylene, fluorenylene, or phenylenediyl.
Heteroaryl, as used herein, refers to the generic term for groups in which one or more of the aromatic nucleus carbons in the arylene group is replaced with a heteroatom, including but not limited to oxygen, sulfur, nitrogen, or phosphorus atoms. Preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms, the heteroarylene group may be attached at a ring-forming carbon atom or at a ring-forming nitrogen atom, and the heteroarylene group may be a monocyclic heteroarylene group, a polycyclic heteroarylene group, or a fused ring heteroarylene group. The monocyclic heteroarylene group includes, but is not limited to, a pyridylene group, a pyrimidinylene group, a triazinylene group, a furanylene group, a thienyl group, and the like; the polycyclic heteroarylene group includes bipyridylene group, bipyrimidiylene group, phenylpyridylene group, etc., but is not limited thereto; the condensed ring heteroarylene group includes quinolinylene, isoquinolylene, indolylene, benzothienyl, benzofuranylene, benzoxazolylene, benzimidazolylene, benzothiazolylene, dibenzofuranylene, benzodibenzofuranylene, dibenzothiophenylene, benzodithiorenylene, carbazolylene, benzocarbazolylene, acridinylene, 9, 10-dihydroacridinylene, phenoxazinylene, phenothiazinylene, phenoxazinylene, and the like, but is not limited thereto. The heteroaryl group is preferably a pyridyl group, a pyrimidylene group, a thienyl group, a furanylene group, a benzothienyl group, a benzofuranylene group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a dibenzodibenzothiophenyl group, a benzodibenzofuranyl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group, or a phenoxathiazide group.
The term "fused ring group" as used herein refers to a generic term for alicyclic and aromatic rings wherein two hydrogen atoms are removed after the alicyclic and aromatic rings are fused together, leaving a divalent group. Preferably having 7 to 30 carbon atoms, more preferably 7 to 18 carbon atoms, and most preferably 7 to 13 carbon atoms, examples may include, but are not limited to, benzobicyclopropyl, benzobicyclobutyl, benzocyclopentylene, benzocyclohexylene, benzocycloheptylene, benzocyclopentylene, benzocyclohexenylene, benzocycloheptylene, naphthocyclopropyl, naphthocyclobutylene, naphthocyclopentyl, naphthocyclohexyl, and the like.
The condensed rings of the aromatic ring and the aliphatic ring according to the present invention mean a ring having one or more aromatic rings and having one or more aliphatic rings condensed with each other by sharing two adjacent carbon atoms in the molecule, the aromatic ring is preferably 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, most preferably 6 to 12 carbon atoms, the aliphatic ring is preferably 3 to 30 carbon atoms, more preferably 3 to 18 carbon atoms, more preferably 3 to 12 carbon atoms, most preferably 3 to 7 carbon atoms, and examples include, but are not limited to, benzocyclopropane group, benzocyclobutane group, benzocyclopentene group, benzocyclohexenyl group, benzocycloheptenyl group, naphthocyclopropane group, naphthocyclobutane group, naphthocyclopentane group, naphthocyclohexenyl group, naphthocyclopentenyl group, naphthocyclohexenyl group, etc.
The aliphatic ring according to the present invention refers to a cyclic hydrocarbon having aliphatic nature, having a closed carbon ring in the molecule, preferably having 3 to 60 carbon atoms, more preferably 3 to 30 carbon atoms, still more preferably 3 to 18 carbon atoms, more preferably 3 to 12 carbon atoms, and most preferably 3 to 7 carbon atoms. Which may form a mono-or polycyclic hydrocarbon, may be fully unsaturated or partially unsaturated, and specific examples may include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclobutene, cyclopentene, cyclohexene, cycloheptene, and the like, but are not limited thereto. The plurality of monocyclic hydrocarbons may also be linked in a variety of ways: two rings in the molecule can share one carbon atom to form a spiro ring; the two carbon atoms on the ring can be connected by a carbon bridge to form a bridge ring; several rings may also be interconnected to form a cage-like structure.
The term "unsubstituted …" as used herein, such as unsubstituted alkyl, unsubstituted cycloalkyl, unsubstituted heterocycloalkyl, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted arylene, unsubstituted heteroarylene, and the like, means that the "hydrogen" (H) in the group is not replaced with other groups including deuterium, tritium, and the like.
"substituted …" as used herein, such as substituted alkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene, and the like, refers to a group that is mono-or poly-substituted with groups independently selected from deuterium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C15 heteroaryl, substituted or unsubstituted amine, and the like, but is not limited thereto, preferably mono-or polysubstituted with groups selected from the group consisting of deuterium, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, camphene, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, perylenyl, pyrenyl, benzyl, tolyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, diphenylamino, dimethylamino, carbazolyl, 9-phenylcarbazolyl, acridinyl, furanyl, thienyl, benzofuranyl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothiophenyl, phenothiazinyl, phenoxazinyl, indolyl. In addition, the substituent may be substituted with one or more substituents selected from deuterium, halogen atom, cyano, alkyl, cycloalkyl and aryl.
The two adjacent substituents can be combined with each other to form a substituted or unsubstituted C3-C8 alicyclic ring, and can be formed into the following substituted or unsubstituted alicyclic ring:
wherein "×" represents the attachment site of the ring.
The linkage described herein to form a substituted or unsubstituted ring means that the two groups are linked to each other by a chemical bond and optionally aromatized. As exemplified below:
in the present invention, the ring formed by the connection may be a five-membered ring or a six-membered ring or a condensed ring, such as benzene, naphthalene, fluorene, cyclopentene, cyclohexene, cyclopentane, cyclohexane acene, quinoline, isoquinoline, dibenzothiophene, phenanthrene or pyrene, but is not limited thereto.
The invention provides a triamine derivative, which has a molecular structural general formula shown in formula I:
wherein the R is 1 、R 2 At least one of which is selected from substituted or unsubstituted C1-C10 alkyl, R 3 A substituent selected from hydrogen, cyano or halogen, and the substituent in the 'substituted or unsubstituted' is selected from one or more of methyl, ethyl, isopropyl and tert-butyl;
the Ar is as follows 1 Selected from the group consisting of substituted or unsubstituted C10-C25 aryl groups wherein the substituents in the "substituted or unsubstituted" are selected from the group consisting of cyano, halogen, methyl, ethyl, One or more of isopropyl and tert-butyl;
the Ar is as follows 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from the group represented by formula a:
the R is m The same or different R is selected from one of hydrogen, cyano, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, or two adjacent R m The groups may be bonded to form a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring, wherein the substituents in "substituted or unsubstituted" are selected from one or more of cyano, halogen, methyl, ethyl, isopropyl, tert-butyl;
the m is 1 Selected from 0, 1, 2, 3, 4 or 5;
the L is 1 、L 2 、L 3 、L 4 、L 5 、L 6 Independently selected from one of single bond, substituted or unsubstituted C6-C25 arylene, wherein the substituent in the "substituted or unsubstituted" is selected from one or more of cyano, halogen, methyl, ethyl, isopropyl and tert-butyl.
Preferably, the three aromatic amine groups in formula I are attached to the benzene ring in meta form to each other.
Preferably, said R 1 、R 2 At least one of which is selected from the group consisting of substituted or unsubstituted: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, wherein the substituents in "substituted or unsubstituted" are selected from methyl, ethyl, isopropyl, tert-butyl.
Preferably, the Ar 1 Any one selected from the following groups:
the R is r The same or different R is selected from one of hydrogen, cyano, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, or two adjacent R r The groups can be bonded to form a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, wherein the substituents in the "substituted or unsubstituted" are selected from one or more of cyano, halogen, methyl, ethyl, isopropyl, tert-butyl;
the r is 1 Selected from 0, 1, 2, 3, 4 or 5; the r is 2 Selected from 0, 1, 2, 3 or 4; the r is 4 Selected from 0, 1, 2, 3, 4, 5, 6 or 7.
Further preferably, the Ar 1 Any one selected from the following groups:
the Rr are the same or different from each other and are selected from hydrogen or one of the following substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, biphenyl, terphenyl, naphthyl; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, phenyl, biphenyl, naphthyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same or different from each other;
The r is 1 Selected from 0, 1, 2, 3, 4 or 5; the r is 2 Selected from 0, 1, 2, 3 or 4; the r is 3 Selected from 0, 1, 2 or 3; the r is 4 Selected from 0, 1, 2, 3, 4, 5, 6 or 7; the r is 5 Selected from 0, 1 or 2; the r is 6 Selected from 0, 1, 2, 3, 4, 5 or 6; the r is 7 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.
Preferably, the Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from any one of the following groups:
the R is m One selected from hydrogen, cyano, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, naphthyl, biphenyl, terphenyl, or optionally two adjacent R m The groups may be bonded together to form a substituted or unsubstituted benzene ring;
wherein said R is m Can also be R mm Substituted, R mm One or more selected from hydrogen, cyano, halogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, anthryl, phenanthryl, triphenylene, and in the case of being substituted with a plurality of substituents, the plurality of substituents may be the same or different from each other;
the m is 1 Selected from 0, 1, 2, 3, 4 or 5; the m is 2 Selected from 0, 1, 2, 3 or 4; the m is 3 Selected from 0, 1, 2 or 3; the m is 4 Selected from 0, 1, 2, 3, 4, 5, 6 or 7; the m is 7 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.
Further preferably, the Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from any one of the following groups:
the R is m Are identical or different from each other and are selected from hydrogen or one of the following substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, biphenyl, terphenyl, naphthyl; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, phenyl, biphenyl, naphthyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same or different from each other;
the m is 1 Selected from 0, 1, 2, 3, 4 or 5; the m is 2 Selected from 0, 1, 2, 3 or 4; the m is 3 Selected from 0, 1, 2 or 3; the m is 4 Selected from 0, 1, 2, 3, 4, 5, 6 or 7; the m is 5 Selected from 0, 1 or 2; the m is 6 Selected from 0, 1, 2, 3, 4, 5 or 6; the m is 7 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.
More preferably, the Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from any one of the following groups:
preferably, the L 1 、L 2 、L 3 、L 4 、L 5 、L 6 Independently selected from a single bond or one of the following groups:
The R is n Any one selected from hydrogen, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C25 aryl; said n 1 Selected from 0, 1, 2, 3 or 4; said n 2 Selected from 0, 1, 2, 3, 4, 5 or 6.
Further preferably, said R n Selected from hydrogen, substituted or unsubstituted: methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, phenyl, naphthyl, anthryl, phenanthryl, triphenyleneWherein the substituent is one or more of methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same as or different from each other.
More preferably, the L 1 、L 2 、L 3 、L 4 、L 5 、L 6 Independently selected from a single bond or one of the following groups:
most preferably, the L 1 、L 2 、L 3 、L 4 、L 5 、L 6 Independently selected from a single bond or one of the following groups:
most preferably, the triamine derivative is selected from any one of the chemical structures shown below:
the preparation method of the triamine derivative shown in the formula I can be prepared through a coupling reaction conventional in the art, for example, the triamine derivative can be prepared through the following synthetic route, but the invention is not limited to the following steps:
The triamine derivative is subjected to Buchwald-Hartwig coupling reaction to obtain intermediates A1, A2 and A3; the raw material e and the intermediate A1 undergo a Buchwald-Hartwig coupling reaction to obtain an intermediate B; intermediate B and intermediate A2 undergo Buchwald-Hartwig coupling reaction to obtain intermediate C, and intermediate C and intermediate A3 undergo Buchwald-Hartwig coupling reaction to finally obtain a compound of formula I, wherein X 1 、X 2 、X 3 、X 4 、X 5 、X 6 Independently represents Cl, br or I.
The source of the raw materials used in the above-mentioned various reactions is not particularly limited in the present invention. The present invention is not particularly limited to the above reaction, and conventional reactions well known to those skilled in the art may be employed.
The invention also provides an organic light-emitting device, which comprises an anode, a cathode and an organic layer, wherein the organic layer is positioned between the anode and the cathode or outside one or more than one of the anode and the cathode, and the organic layer contains any one or a combination of at least two of the triamine derivatives.
Preferably, the organic layer comprises a hole transport region, a light emitting layer, an electron transport region, and a capping layer, and at least one of the hole transport region, the light emitting layer, and the capping layer contains any one or a combination of at least two of the triamine derivatives described in the present invention.
Preferably, the organic layer comprises a hole transport region between the anode and the light-emitting layer, wherein the hole transport region contains any one or a combination of at least two of the triamine derivatives of the present invention.
Preferably, the hole transport region comprises a hole transport layer, the hole transport layer is positioned between the anode and the light-emitting layer, and the hole transport layer contains any one or a combination of at least two of the triamine derivatives disclosed by the invention.
Preferably, the hole transport region comprises a hole transport layer and/or a light-emitting auxiliary layer (second hole transport layer), the light-emitting auxiliary layer being located between the hole transport layer and the light-emitting layer, and the hole transport layer and/or the light-emitting auxiliary layer comprising any one or a combination of at least two of the triamine derivatives described in the present invention.
Preferably, the organic layer comprises a light-emitting layer, the light-emitting layer is positioned between the hole transport region and the electron transport region, and the light-emitting layer contains any one or a combination of at least two of the triamine derivatives.
Preferably, the light-emitting layer comprises a host material and/or a doping material, and the host material contains any one or a combination of at least two of the triamine derivatives.
Preferably, the organic layer comprises an electron transport region, the electron transport region is located between the light emitting layer and the cathode, and the electron transport region contains any one or a combination of at least two of the triamine derivatives of the present invention.
Preferably, the electron transport region comprises an electron transport layer, the electron transport layer is located between the light emitting layer and the cathode, and the electron transport layer contains any one or a combination of at least two of the triamine derivatives of the present invention.
Preferably, the electron transport region comprises an electron transport layer and/or a hole blocking layer, the hole blocking layer is positioned between the light emitting layer and the electron transport layer, and any one or at least two of the triamine derivatives disclosed by the invention are contained in the electron transport layer and/or the hole blocking layer.
The light emitting device of the present invention is generally formed on a substrate. The substrate may be a substrate made of glass, plastic, polymer film, silicon, or the like, as long as it is not changed when an electrode is formed or an organic layer is formed. When the substrate is opaque, the electrode opposite thereto is preferably transparent or translucent.
Anode materials, typically selected from materials having a high work function, facilitate hole injection. The anode may be a reflective electrode or a transmissive electrode. The material for the anode may be a transparent and highly conductive material, for example, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin oxide (SnO) 2 ) And zinc oxide (ZnO), the structure of the anode material is not limited thereto. When the anode is a semi-transmissive electrode or a reflective electrode, as a material for forming the anode, at least one selected from magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag) may be used.
The anode may have a single-layer structure or a multi-layer structure including two or more layers. For example, the anode may have a three-layer structure of ITO/Ag/ITO, but the structure of the anode is not limited thereto. Preferably, the anode of the present invention adopts a transparent ITO substrate. The anode may be formed by depositing or spraying a material for forming the anode on the substrate.
The hole transport region may include a single layer structure of a plurality of different materials, a structure of a hole injection layer/hole transport layer/buffer layer, a structure of a hole injection layer/buffer layer, a structure of a hole transport layer/buffer layer, or a structure of a hole injection layer/hole transport layer/electron blocking layer, wherein layers of the respective structures are sequentially stacked in the stated order from the anode, but the structure of the hole transport region is not limited thereto.
The hole injection material is a material having a function of promoting injection of holes from the anode. The hole injection layer may be formed at a thickness in the range of 10nm to 150 nm. The material of the hole injection layer may include polyetherketone (tpappek) containing triphenylamine, 4-isopropyl-4 ' -methyldiphenyliodonium tetrakis (pentafluorophenyl) borate (PPBI), N ' -diphenyl-N, N ' -bis- [4- (phenyl-m-tolyl-amino) -phenyl ] -biphenyl-4, 4' -diamine (DNTPD), copper (II) phthalocyanine (abbreviation: cuPc), 4',4″ -tris (3-methylphenyl phenylamino) triphenylamine (m-MTDATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (abbreviation: HAT-CN), 4',4 "-tris { N, N-diphenylamino } triphenylamine (TDATA), 4',4" -tris (N, N-2-naphthylphenylamino) triphenylamine (2-TNATA), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (PANI/CSA) or polyaniline/poly (4-styrenesulfonate (PANI/PSS) and the like, may be a single structure composed of a single substance, or may be a single-layer or multi-layer structure formed of different substances, other known materials suitable for the hole injection layer may also be selected.
The hole transport material is a material having a good hole transport property, and the hole transport layer can be formed to a layer thickness of 10nm to 150nm (for example, the total layer thickness of the multilayer structure). The hole transport layer material may be selected from polymer materials such as aromatic amine derivatives, carbazole derivatives, stilbene derivatives, triphenyldiamine derivatives, styrene compounds, butadiene compounds, and the like, and polymer materials such as polyparaphenylene derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, and the like, but is not limited thereto. Examples of the hole transporting material may include 1, 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC), carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, N '-bis (3-methylphenyl) -N, N' -diphenyl- [1, 1-biphenyl ] -4,4 '-diamine (TPD), 4',4 "-tris (N-carbazolyl) triphenylamine (TCTA), N '-bis (1-naphthyl) -N, N' -diphenylbenzidine (NPB), 2, 7-tetrakis (diphenylamino) -9, 9-spirobifluorene (abbreviation: spiro-TAD), and the like. Preferably, the hole transport layer is selected from the triamine derivatives according to the present invention, and may be a single structure formed of a single substance, or may be a single layer structure formed of different substances, or may be a multi-layer structure, and the hole transport layer may include a single layer, or may include a first hole transport layer and a second hole transport layer, or may include more layers. One or more layers of the hole transport layers contain the triamine derivative provided by the invention, the first hole transport layer is positioned between the hole injection layer and the light-emitting layer, and the second hole transport layer is positioned between the first hole transport layer and the light-emitting layer.
The light-emitting layer is a layer having a light-emitting function, and includes a host material and a dopant material, and emits light by fluorescence or phosphorescence. The light emitting layer may be formed to have a layer thickness in the range of 10nm to 60 nm. The light emitting layer may be formed to have a layer emitting light of a specific color. For example, the light emitting layer may be formed as a red light emitting layer, a green light emitting layer, or a blue light emitting layer.
The host material is selected from 4,4 '-bis (9-Carbazole) Biphenyl (CBP), 9, 10-bis (2-naphthyl) Anthracene (ADN), 4-bis (9-carbazolyl) biphenyl (CPB), 9' - (1, 3-phenyl) bis-9H-carbazole (mCP), 4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (α -AND), N' -bis- (1-naphthyl) -N, N '-diphenyl- [1,1':4',1": 4',1 '-tetrabenzoyl ] -4, 4' -diamine group (4 PNPB), 1,3, 5-tris (9-carbazolyl) benzene (TCP), AND the like. In addition to the above materials and combinations thereof, the host material of the light-emitting layer may be selected from the triamine derivatives provided by the present invention, and other known materials suitable for use as the light-emitting layer may be selected.
In the case where the light emitting layer is a blue light emitting layer, a suitable blue dopant may be used. For example, perylenes and derivatives thereof, iridium (Ir) complexes such as bis [2- (4, 6-difluorophenyl) pyridine (pyridinate)]Iridium (III) picolinate (FIrpic) may be used as a blue dopant. In the case where the light emitting layer is a red light emitting layer, a suitable red dopant may be used. For example rubrene and its derivatives, 4-dicyanomethylene-2- (p-dimethylaminostyryl) -6-methyl-4H-pyran (DCM) and its derivatives, iridium complexes such as bis (1-phenylisoquinoline) (acetylacetonate) iridium (III) (Ir (piq) 2 (acac), osmium (Os) complexes, platinum complexes, and the like can be used as red dopants. When the light emitting layer is a green light emitting layer, a suitable green dopant may be used. For example, coumarin and its derivatives, iridium complexes such as tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3 ) Etc.
The doping ratio of the host material and the guest material of the light-emitting layer may be varied depending on the materials used, and the doping ratio of the guest material of the light-emitting layer is usually 0.01 to 20%, preferably 0.1 to 15%, more preferably 1 to 10%.
The electron transport region may include at least one of an electron injection layer, an electron transport layer, a buffer layer, and a hole blocking layer. The electron transport layer may be a single structure formed of a single material, a single layer structure formed of different materials, or a multi-layer structure, and the electron transport layer may include a single layer, or may include a first electron transport layer and a second electron transport layer or more. The type of the electron transport region may be an electron injection layer/electron transport layer structure, an electron injection layer/electron transport layer/buffer layer structure, an electron injection layer/buffer layer structure, or an electron injection layer/electron transport layer/hole blocking layer structure, in which layers of the respective structures are stacked one after another in the stated order from the cathode, but the structure of the electron transport region is not limited thereto.
The hole blocking layer is effective to prevent exciton from escaping to the hole transport layer, and preferably has a high triplet level and a suitable HOMO level, and can be formed to have a layer thickness in the range of 15nm to 50 nm. Examples of the hole blocking layer may include: oxadiazole derivatives, triazole derivatives, quinoline derivatives, phenanthroline derivatives, anthraquinone derivatives, anthrone derivatives, azabenzene derivatives, imidazole derivatives, and the like, but are not limited thereto. Preferably, the hole blocking material is selected from the heterocyclic compounds provided by the present invention.
The electron transport layer is a layer having an electron transport function. The electron transport layer may be formed to a layer thickness in the range of 15nm to 50 nm. The electron transport layer material may be selected from quinoline derivatives such as tris (8-hydroxyquinoline) aluminum (Alq 3), 1,2, 4-triazole derivatives (TAZ), bis (2-methyl-8-hydroxyquinolino) - (p-phenylphenolato) -aluminum (BAlq), bis (10-hydroxybenzoquinoline) beryllium (BeBq 2), li complexes such as 8-hydroxyquinoline Lithium (LiQ), nitrogen-containing aromatic rings, and the like, and examples of the nitrogen-containing aromatic rings may include pyridine ring-containing materials such as 1,3, 5-tris [ (3-pyridyl) -benzene-3-yl ] benzene, triazine ring-containing materials such as 2,4, 6-tris (3' - (pyridin-3-yl) biphenyl-3-yl) -1,3, 5-triazine, imidazole derivative-containing materials such as 2- (4- (N-phenylbenzimidazolyl-1-ylphenyl) -9, 10-dinaphthyl anthracene, and the like. It may be a single structure composed of a single substance, or may be a single-layer structure or a multi-layer structure formed of different substances. In addition to the above materials, the electron transport layer may be selected from the heterocyclic compounds provided by the present invention, and other known materials suitable for use as an electron transport layer may be selected.
The electron injection layer is a layer having a function of promoting electron injection from the cathode. The electron injection layer may be formed to have a layer thickness in the range of 0.3nm to 9 nm. The electron injection layer material can be selected from lithium fluoride (LiF), sodium chloride (NaCl), cesium fluoride (CsF), lithium oxide (Li) 2 O), barium oxide (BaO), lithium 8-hydroxyquinoline (LiQ), and the like. In addition to the above materials, the electron injection layer may be selected from the heterocyclic compounds provided by the present invention, and other known materials suitable for use as an electron injection layer may be selected.
Preferably, the electron transport region contains a heterocyclic compound represented by formula ii:
the Arb and Arc are the same or different and are selected from structures shown in a formula b,
z is selected from any one of O, S or N (Ry); the Ry is selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
the Y is the same or different and is selected from C (Rx) or N; the Rx is the same or different and is selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent Rx are connected to form a substituted or unsubstituted ring;
The R is b 、R c Independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, fused ring group of substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring, substituted or unsubstituted C2-C30 heteroaryl, or R b 、R c Can be combined with each other to form a substituted or unsubstituted spiro ring; r is R b 、R c Any one of which can be directly bonded to the bridging La;
the R is 0 Any one selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; the a is selected from 0, 1, 2 or 3;
the R is a 、R t Independently selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C3-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; or two adjacent R a May be linked to form a substituted or unsubstituted aromatic or aliphatic ring; or two adjacent R t May be linked to form a substituted or unsubstituted aromatic or aliphatic ring;
the a 1 Selected from 0, 1, 2, 3 or 4; the a 2 Selected from 0, 1, 2, 3 or 4; said t is selected from 0, 1, 2, 3 or 4;
the L is a 、L b 、L c The same or different one selected from single bond, substituted or unsubstituted arylene of C6-C30, substituted or unsubstituted heteroarylene of C2-C30, substituted or unsubstituted alicyclic of C3-C10 and condensed ring group of aromatic ring of C6-C25.
Preferably, said R t Identical to or different from each other, selected from hydrogen, deuterium or one of the following substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, canyl, norbornyl, phenyl, biphenyl, naphthyl, anthryl, phenanthryl, triphenylyl, cyano, fluoro, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzocyclopentenyl, benzocyclohexenyl, benzocyclopentenyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, methylphenidateOne of an oxazinyl group, an oxazolidinyl group, a thiazolidinyl group and an imidazolidinyl group; or two adjacent R t Can be connected to form benzene ring, naphthalene ring or three-to eight-membered aliphatic ring; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of deuterium, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, cananyl, norbornyl, phenyl, biphenyl, naphthyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same as or different from each other.
More preferably, the formula b is selected from one of the structural groups shown:
preferably, said R b 、R c Independently selected from any of hydrogen, deuterium, substituted or unsubstituted: C1-C6 alkyl, C3-C7 cycloalkyl, adamantyl, norbornyl, C6-C12 aryl, C2-C12 heteroaryl, benzocyclopentenyl, benzocyclohexenyl, benzocyclopentenyl, naphthocyclohexenyl, naphthocyclopentenyl, naphthocyclohexenyl; the substituent groups are selected from any one or more of deuterium, C1-C12 alkyl and C3-C12 cycloalkyl;
Or said R b 、R c Any one of the following spiro structures may be formed:
the R is p Selected from hydrogen, deuterium or substituted or unsubstituted groups of: methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, phenanthryl, triphenylene, dibenzofuranyl, dibenzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, substituted by one or more of deuterium, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, deuterated isopropyl, deuterated tert-butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated cyclobutyl, deuterated cyclopropyl, deuterated adamantyl, deuterated norbornyl, deuterated phenyl, deuterated naphtyl, deuterated biphenyl, or adjacent R p Can be bonded to form a benzene ring or naphthalene ring;
the p is 1 Selected from 0, 1 or 2; p is p 2 Selected from 0, 1, 2, 3 or 4; p is p 3 Selected from 0, 1, 2, 3, 4, 5 or 6; p is p 4 Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; p is p 5 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; p is p 6 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; p is p 7 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.
Preferably, the said
Any one selected from the following groups:
the a is selected from 0, 1, 2 or 3; b is selected from 0, 1, 2, 3 or 4; c is selected from 0, 1, 2, 3, 4 or 5; e is selected from 0, 1, 2, 3, 4, 5 or 6; d is selected from 0, 1, 2, 3, 4, 5, 6 or 7; f is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; g is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; h is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; i is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.
Preferably, said R a Selected from deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, anthracenyl, phenanthryl, triphenylene, dibenzofuranyl, dibenzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl, pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, piperazinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, and may also be substituted with deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, deuterated isopropyl, deuterated tert-butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated cyclobutyl, deuterated cyclopropyl, deuterated adamantyl, deuterated norbornyl, deuterated naphthyl, or a plurality of deuterated naphthalenes.
Preferably, said R a Selected from the group consisting of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, t-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, deuterated isopropyl, deuterated t-butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated cyclobutyl, deuterated cyclopropyl, deuterated goldAn adamantyl group, a deuterated norbornyl group, or one of the following groups:
preferably, the L a 、L b 、L c The same or different is selected from single bond or any one of the structures shown below,
wherein the R is 9 The same or different is selected from any one of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, anthryl, phenanthryl, triphenylene, dibenzofuranyl, dibenzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl, and may be further substituted with one or more of deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, deuterated isopropyl, deuterated tert-butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated cyclobutyl, deuterated cyclopropyl, deuterated adamantyl, deuterated norbornyl, deuterated biphenyl;
The R is 4 The same or different groups are selected from deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, anthryl, phenanthryl, triphenylene, and diphenylBenzofuranyl, dibenzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl, and any of the above groups may also be substituted with one or more of deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, t-butyl, cyclohexyl, cyclopentyl, adamantyl, norbornyl, phenyl, naphthyl, biphenyl, terphenyl, deuterated isopropyl, deuterated t-butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated phenyl, deuterated naphthyl, deuterated biphenyl;
the k is 1 Selected from 0, 1, 2, 3 or 4, k 2 Selected from 0, 1, 2, 3, 4, 5 or 6,k 3 Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, k 4 Selected from 0, 1, 2 or 3, k 5 Selected from 0, 1 or 2, k 6 Selected from 0, 1, 2, 3, 4 or 5; when k is 1 、k 2 、k 3 、k 4 、k 5 、k 6 Above 1, two or more R 9 The same as or different from each other.
Most preferably, the heterocyclic compound is selected from any one of the chemical structures shown below:
The preparation method of the heterocyclic compound of the formula II can be prepared through coupling reaction conventional in the art, for example, can be prepared through the following synthetic route, but the invention is not limited thereto:
the heterocyclic compound is subjected to Suzuki coupling reaction to finally obtain the compound of the formula II, wherein Xa, xb, xc, xd, xe, xf, xg independently represents Cl, br or I.
The source of the raw materials used in the above-mentioned various reactions is not particularly limited in the present invention. The present invention is not particularly limited to the above reaction, and conventional reactions well known to those skilled in the art may be employed.
The cathode electrode is an electron injection/transport layer or a light emitting layer, and may be formed as a reflective electrode using a metal, an alloy, a conductive compound, or the like having a low work function. The cathode may be formed using, for example, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag). The cathode may be formed as a thin film of a material having a thickness of about 20nm or less, and may be formed as a transmissive electrode using ITO, IZO, or the like. The film can be produced by forming a thin film by vapor deposition, sputtering, or the like, and the film thickness is usually 10nm to 1. Mu.m, preferably 50 to 200nm.
The cladding material is to reduce total emission loss and waveguide loss in the OLED device and to improve light extraction efficiency. The coating material of the present invention may be Alq 3 TPBi, etc., other known materials suitable for use as a capping layer, and the triamine derivatives of the present invention may be selected.
The method for preparing and forming each layer in the organic light emitting device is not particularly limited, and any one of vacuum evaporation method, spin coating method, vapor deposition method, blade coating method, laser thermal transfer method, electrospray coating method, slit coating method, and dip coating method may be used, and in the present invention, a vacuum evaporation method is preferably used.
The organic light-emitting device can be widely applied to the fields of panel display, illumination light sources, flexible OLED, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, indication boards, signal lamps and the like.
The present invention is explained more fully by the following examples, but is not intended to be limited thereby. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue burden.
Preparation and characterization of the Compounds
Description of the starting materials, reagents and characterization equipment:
the source of the raw materials used in the following examples is not particularly limited and may be commercially available products or prepared by a preparation method well known to those skilled in the art.
The mass spectrum uses a Wotes G2-Si quadrupole tandem time-of-flight high resolution mass spectrometer in UK, chloroform as a solvent;
the elemental analysis was carried out using a Vario EL cube organic elemental analyzer from Elementar, germany, and the sample mass was 5 to 10mg.
Synthesis example 1 Synthesis of Compound 8
Synthesis of A1-8:
to the reaction flask were added a1-8 (130.00 mmol,20.41 g), intermediate b1-8 (140 mmol,13.04 g), 1' -bis-diphenylphosphino ferrocene palladium dichloride (1.30 mmol,0.95 g), sodium t-butoxide (195.00 mmol,18.74 g) under nitrogen protection, followed by 350mL of toluene, and the reaction was heated under reflux for 5 hours. After the reaction was completed, cooled to room temperature, water was added, extraction was performed with methylene chloride, the organic layer was dried over anhydrous magnesium sulfate, filtration was performed, the solvent was concentrated by distillation under reduced pressure, and recrystallization was performed with ethyl acetate to obtain intermediate A1-8 (17.60 g, yield 80%), and the purity of the solid was not less than 99.29% by HPLC detection. Mass spectrum m/z:169.0880 (theory: 169.0891).
Synthesizing A2-8:
a1-8 was replaced with equimolar A2-8 according to the same preparation method as A1-8 to give A2-8 (30.34 g, yield 79%) with a purity of not less than 99.48% as measured by HPLC. Mass spectrum m/z:295.1374 (theory: 295.1361).
Synthesizing B-8:
e-8 (45.00 mmol,12.69 g), A2-8 (50.00 mmol,14.77 g), palladium acetate (0.45 mmol,0.10 g), tri-tert-butylphosphine (1.80 mL of 0.5M toluene solution, 0.90 mmol), sodium tert-butoxide (90.00 mmol,8.65 g) and 200mL toluene were added to the flask under nitrogen, and the mixture was stirred and heated to reflux for 6 hours. After the reaction was completed, cooled to room temperature, water was added, extracted with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was concentrated by distillation under reduced pressure, and purified by silica gel column chromatography (dichloromethane: n-hexane=1:4) to give B-8 (17.43 g, yield 78%), and the purity of the solid was not less than 99.65% by HPLC detection. Mass spectrum m/z:495.1533 (theory: 495.1521).
Synthesis of Compound 8:
to the reaction flask was added B-8 (30.00 mmol,14.89 g), A2-8 (65.00 mmol,19.20 g), dibenzylideneacetone dipalladium (0.30 mmol,0.27 g), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (0.60 mmol,0.29 g), sodium t-butoxide (60.00 mmol,5.77 g) and 300mL toluene under nitrogen, and the mixture was stirred and heated to reflux for 5.5 hours. After the reaction was completed, cooled to room temperature, water was added, extraction was performed with methylene chloride, the organic layer was dried over anhydrous magnesium sulfate, filtration was performed, the solvent was concentrated by distillation under reduced pressure, and recrystallization was performed with toluene to obtain compound 8 (17.60 g, yield 77%), and the purity of the solid was not less than 99.98% by HPLC detection. Mass spectrum m/z:761.3785 (theory: 761.3770). Theoretical element content (%) C 56 H 47 N 3 : c,88.27; h,6.22; n,5.51. Measured element content (%): c,88.23; h,6.25; n,5.53.
Synthesis example 2 Synthesis of Compound 22
According to the same production method as that of Synthesis example 1, a1-8 was replaced with equimolar a1-22, a2-8 was replaced with equimolar a2-22, b1-8 was replaced with equimolar b2-22, and e-8 was replaced with equimolar e-22, to obtain Compound 22 (19.94), and the purity of the solid was not less than 99.95% as measured by HPLC. Mass spectrum m/z:885.5033 (theoretical value: 885.5022). Theoretical element content (%) C 65 H 63 N 3 : c,88.09; h,7.17; n,4.74. Measured element content (%): c,88.05; h,7.18; n,4.77.
Synthesis example 3 Synthesis of Compound 49
Synthesis of A1-49:
according to the same production method as that of A1-8 in example 1, A1-8 was replaced with equimolar A1-49 and b1-8 was replaced with equimolar b1-49 to obtain A1-49 (26.29 g, yield 78%), and the purity of the solid was not less than 99.46% by HPLC detection. Mass spectrum m/z:259.1355 (theory: 259.1364).
Synthesis of Compound 49:
to the reaction flask was added e-49 (30.00 mmol,5.86 g), A1-49 (95.00 mmol,24.64 g), dibenzylideneacetone dipalladium (0.40 mmol,0.37 g), tri-tert-butylphosphine (1.40 mL of a 0.5M toluene solution, 0.70 mmol), sodium tert-butoxide (70.00 mmol,6.73 g) and 350mL toluene under nitrogen, and the mixture was stirred and heated to reflux for 7 hours. After the reaction was completed, cooled to room temperature, water was added, extraction was performed with methylene chloride, the organic layer was dried over anhydrous magnesium sulfate, filtration was performed, the solvent was concentrated by distillation under reduced pressure, and recrystallization was performed with toluene to obtain compound 49 (20.48 g, yield 79%), and the purity of the solid was not less than 99.96% by HPLC detection. Mass spectrum m/z:863.4248 (theory: 863.4239). Theoretical element content (%) C 64 H 53 N 3 : c,88.96; h,6.18; n,4.86. Measured element content (%): c,88.99; h,6.16; n,4.85.
Synthesis example 4 Synthesis of Compound 66
According to the same manner as that of Synthesis example 3 except that a1-49 was replaced with equimolar a1-66 and b1-49 was replaced with equimolar b1-8, compound 66 (19.73 g) was obtained, and the purity of the solid was not less than 99.95 as measured by HPLCPercent of the total weight of the composition. Mass spectrum m/z:821.3785 (theory: 821.3770). Theoretical element content (%) C 61 H 47 N 3 : c,89.13; h,5.76; n,5.11. Measured element content (%): c,89.15; h,5.73; n,5.13.
Synthesis example 5 Synthesis of Compound 69
According to the same manner as that of Synthesis example 3 except that a1-49 was replaced with equimolar a1-66 and b1-49 was replaced with equimolar b1-69, compound 69 (21.10 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.97%. Mass spectrum m/z:989.5661 (theory: 989.5648). Theoretical element content (%) C 73 H 71 N 3 : c,88.53; h,7.23; n,4.24. Measured element content (%): c,88.55; h,7.25; n,4.20.
Synthesis example 6 Synthesis of Compound 85
According to the same manner as that of Synthesis example 3 except that a1-49 was replaced with equimolar a2-22 and b1-49 was replaced with equimolar b1-85, compound 85 (21.43 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.98%. Mass spectrum m/z:1049.4718 (theory: 1049.4709). Theoretical element content (%) C 79 H 59 N 3 : c,90.34; h,5.66; n,4.00. Measured element content (%): c,90.33; h,5.65; n,4.02.
Synthesis example 7 Synthesis of Compound 175
According to the same manner as that of Synthesis example 3 except that a1-49 was replaced with equimolar a1-66 and b1-49 was replaced with equimolar b1-8,e-49 with equimolar e-175, compound 175 (19.12 g) was obtained, HPLC analysisThe purity of the measured solid is more than or equal to 99.97 percent. Mass spectrum m/z:849.4097 (theory: 849.4083). Theoretical element content (%) C 63 H 51 N 3 : c,89.01; h,6.05; n,4.94. Equimolar measured element content (%): c,89.04; h,6.04; n,4.92.
Synthesis example 8 Synthesis of Compound 232
According to the same production method as that of Synthesis example 1, a1-8 was replaced with equimolar a1-69, a2-8 was replaced with equimolar a2-232, b1-8 was replaced with equimolar b1-49, and e-8 was replaced with equimolar e-232, to obtain Compound 232 (19.03 g), and the purity of the solid as measured by HPLC was not less than 99.96%. Mass spectrum m/z:905.4718 (theory: 905.4709). Theoretical element content (%) C 67 H 59 N 3 : c,88.80; h,6.56; n,4.64. Measured element content (%): c,88.85; h,6.51; n,4.63.
Synthesis example 9 Synthesis of Compound 242
According to the same manner as that of Synthesis example 1 except that a2-8 was replaced with equimolar a2-242, b1-8 was replaced with equimolar b1-49 and e-8 was replaced with equimolar e-232, compound 242 (19.05 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.94%. Mass spectrum m/z:857.4720 (theory: 857.4709). Theoretical element content (%) C 63 H 59 N 3 : c,88.17; h,6.93; n,4.90. Measured element content (%): c,88.15; h,6.90; n,4.95.
Synthesis example 10 Synthesis of Compound 246
Following the same procedure as in Synthesis example 1, a was followed1-8 is replaced by equimolar a1-66, a2-8 is replaced by equimolar a2-246, e-8 is replaced by equimolar e-232, and compound 246 (18.34 g) is obtained, and the purity of the solid detected by HPLC is more than or equal to 99.97%. Mass spectrum m/z:773.3785 (theory: 773.3770). Theoretical element content (%) C 57 H 47 N 3 : c,88.45; h,6.12; n,5.43. Measured element content (%): c,88.42; h,6.18; n,5.40.
Synthesis example 11 Synthesis of Compound 259
According to the same production method as that of Synthesis example 1, a1-8 was replaced with equimolar a1-66, b1-8 was replaced with equimolar b1-49, a2-8 was replaced with equimolar a1-8,e-8 and with equimolar e-232, to obtain Compound 259 (18.86 g), and the purity of the solid as measured by HPLC was not less than 99.97%. Mass spectrum m/z:897.4072 (theory: 897.4083). Theoretical element content (%) C 67 H 51 N 3 : c,88.60; h,5.72; n,4.68. Measured element content (%): c,88.65; h,5.70; n,4.65.
Synthesis example 12 Synthesis of Compound 269
According to the same production method as that of Synthesis example 1, a1-8 was replaced with equimolar a1-66, a2-8 was replaced with equimolar a2-269, and e-8 was replaced with equimolar e-232, to obtain Compound 269 (19.34 g), and the purity of the solid was not less than 99.98% as measured by HPLC. Mass spectrum m/z:795.3623 (theory: 795.3613). Theoretical element content (%) C 59 H 45 N 3 : c,89.02; h,5.70; n,5.28. Measured element content (%): c,89.05; h,5.74; n,5.21.
Synthesis example 13 Synthesis of Compound 278
According to the same manner as that of Synthesis example 1 except that a1-8 was replaced with equimolar a1-278 and a2-8 was replaced with equimolar a2-278 and e-8 was replaced with equimolar e-232, compound 278 (22.65 g, 73%) was obtained and the purity of the solid as determined by HPLC was not less than 99.95%. Mass spectrum m/z:1033.5325 (theory: 1033.5335). Theoretical element content (%) C 77 H 67 N 3 : c,89.41; h,6.53; n,4.06. Measured element content (%): c,89.47; h,6.51; n,4.03.
Synthesis example 14 Synthesis of Compound 306
According to the same manner as that of Synthesis example 1 except that a1-8 was replaced with equimolar a1-306 and a2-8 was replaced with equimolar a1-8,e-8 with equimolar e-232, compound 306 (21.63 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.94%. Mass spectrum m/z:897.4094 (theory: 897.4083). Theoretical element content (%) C 67 H 51 N 3 : c,89.60; h,5.72; n,4.68. Measured element content (%): c,89.63; h,5.70; n,4.66.
Synthesis example 15 Synthesis of Compound 317
According to the same manner as that of Synthesis example 1 except that a1-8 was replaced with equimolar a1-317, a2-1 was replaced with equimolar a2-237 and e-8 was replaced with equimolar e-232, compound 317 (23.06 g) was obtained, and the purity of the solid was not less than 99.98% as measured by HPLC. Mass spectrum m/z:997.4388 (theory: 997.4396). Theoretical element content (%) C 75 H 55 N 3 : c,90.24; h,5.55; n,4.21. Measured element content (%): c,90.28; h,5.51; n,4.21.
Synthesis example 16 Synthesis of Compound 343
According to the same production method as that of Synthesis example 1, a2-8 was replaced with equimolar a2-343, and e-8 was replaced with equimolar e-343, to obtain Compound 343 (19.24 g), and the purity of the solid was not less than 99.97% by HPLC. Mass spectrum m/z:821.3785 (theory: 821.3770). Theoretical element content (%) C 61 H 47 N 3 : c,89.13; h,5.76; n,5.11. Measured element content (%): c,89.15; h,5.77; n,5.08.
Synthesis example 17 Synthesis of Compound 351
According to the same production method as that of Synthesis example 1, a1-8 was replaced with equimolar a1-66, a2-8 was replaced with equimolar a2-351, and e-8 was replaced with equimolar e-343, to obtain Compound 351 (19.67 g), and the purity of the solid was not less than 99.96% as measured by HPLC. Mass spectrum m/z:897.4095 (theory: 897.4083). Theoretical element content (%) C 67 H 51 N 3 : c,89.60; h,5.72; n,4.68. Measured element content (%): c,89.63; h,5.74; n,4.63.
Synthesis example 18 Synthesis of Compound 367
According to the same production method as that of Synthesis example 1, a1-8 was replaced with equimolar a2-22, a2-8 was replaced with equimolar a2-367, and e-8 was replaced with equimolar e-367, to obtain Compound 367 (21.27 g), and the purity of the solid as measured by HPLC was not less than 99.95%. Mass spectrum m/z:885.4071 (theory: 885.4083). Theoretical element content (%) C 66 H 51 N 3 : c,89.46; h,5.80; n,4.74. Measured element content (%): c,89.43; h,5.85; n,4.72.
Synthesis example 19 Synthesis of Compound 413
According to the same manner as that of Synthesis example 1 except that a1-8 was replaced with equimolar a1-66, a2-8 was replaced with equimolar a2-413 and e-8 was replaced with equimolar e-413, compound 413 (21.00 g) was obtained, and the purity of the solid was not less than 99.98% as measured by HPLC. Mass spectrum m/z:885.4091 (theory: 885.4083). Theoretical element content (%) C 66 H 51 N 3 : c,89.46; h,5.80; n,4.74. Measured element content (%): c,89.47; h,5.85; n,4.68.
Synthesis example 20 Synthesis of Compound 421
According to the same manner as that of Synthesis example 1, b1-8 was replaced with equimolar b2-22, a2-8 was replaced with equimolar a2-421, and e-8 was replaced with equimolar e-413, to give Compound 421 (22.24 g), which was found to have a solid purity of 99.97% or more by HPLC. Mass spectrum m/z:987.4541 (theory: 987.4552). Theoretical element content (%) C 74 H 57 N 3 : c,89.93; h,5.81; n,4.25. Measured element content (%): c,89.95; h,5.85; n,4.20.
Synthesis example 21 Synthesis of Compound 502
According to the same manner as that of Synthesis example 1 except that a1-8 was replaced with equimolar a1-66, a2-8 was replaced with equimolar a2-502 and e-8 was replaced with equimolar e-232, compound 502 (21.21 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.96%. Mass spectrum m/z:897.4096 (theory: 897.4083). Theoretical element content (%) C 67 H 51 N 3 : c,89.60; h,5.72; n,4.68. Measured element content (%): c,89.58;H,5.75；N,4.67。
synthesis example 22 Synthesis of Compound 504
According to the same production method as that of Synthesis example 3, substituting a1-49 with equimolar a2-269 and b1-49 with equimolar b1-504, compound 504 (18.68 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.95%. Mass spectrum m/z:893.3783 (theory: 893.3770). Theoretical element content (%) C 67 H 47 N 3 : c,90.00; h,5.30; n,4.70. Measured element content (%): c,90.02; h,5.26; n,4.72.
Synthesis example 23 Synthesis of Compound 506
According to the same manner as that of Synthesis example 1 except that a2-8 was replaced with equimolar a1-8, b1-8 was replaced with equimolar b2-506, and e-8 was replaced with equimolar e-232, compound 506 (19.21 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.97%. Mass spectrum m/z:743.3312 (theory: 743.3300). Theoretical element content (%) C 55 H 41 N 3 : c,88.80; h,5.56; n,5.65. Measured element content (%): c,88.83; h,5.55; n,5.62.
Synthesis example 24 Synthesis of Compound 507
According to the same manner as that of Synthesis example 1 except that a1-8 was replaced with equimolar a1-66 and a2-8 was replaced with equimolar a1-8,e-8 with equimolar e-507, compound 507 (16.40 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.97%. Mass spectrum m/z:759.3624 (theory: 759.3613). Theoretical element content (%) C 56 H 45 N 3 ：C,88.50; h,5.97; n,5.53. Measured element content (%): c,88.53; h,5.95; n,5.52.
Synthesis example 25 Synthesis of Compound 511
The preparation of intermediates A1-8, the preparation of intermediates A1-66 and the preparation of intermediates A3-511 were obtained in the same manner as in the preparation of intermediates A1-8 of Synthesis example 1.
Synthesis B-511:
to the reaction flask were added e-511 (80.00 mmol,26.51 g), A1-66 (85.00 mmol,20.85 g), palladium acetate (0.80 mmol,0.18 g), tri-tert-butylphosphine (3.00 mL of 0.5M toluene solution, 1.50 mmol), sodium tert-butoxide (200.00 mmol,19.22 g) and 300mL toluene under nitrogen, and the mixture was stirred and heated for 5.5 hours under reflux. After the reaction was completed, cooled to room temperature, water was added, extracted with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was concentrated by distillation under reduced pressure, and purified by silica gel column chromatography (dichloromethane: n-hexane=1:4) to give B-511 (24.41 g, yield 68%), and the purity of the solid was not less than 99.68% by HPLC detection. Mass spectrum m/z:447.0398 (theory: 447.0389).
Synthesis C-511:
to the reaction flask were added B-511 (50.00 mmol,22.44 g), A1-8 (55.00 mmol,9.31 g), palladium acetate (0.75 mmol,0.17 g), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (1.50 mmol,0.72 g), sodium t-butoxide (100.00 mmol,9.61 g) and 300mL of toluene under nitrogen atmosphere, and the mixture was stirred and heated to reflux for 5 hours. After the reaction was completed, cooled to room temperature, water was added, extracted with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was concentrated by distillation under reduced pressure, and purified by silica gel column chromatography (dichloromethane: petroleum ether=3:8) to give C-511 (20.95 g, yield 78%), and the purity of the solid was not less than 99.77% by HPLC detection. Mass spectrum m/z:536.2044 (theory: 536.2019).
Synthesis of Compound 511:
under the protection of nitrogen, C-51 is added into a reaction bottle1 (30.00 mmol,16.11 g), A3-511 (35.00 mmol,11.25 g), dibenzylideneacetone dipalladium (0.30 mmol,0.28 g), tri-tert-butylphosphine (1.20 mL of 0.5M toluene solution, 0.60 mmol), sodium tert-butoxide (60.00 mmol,5.77 g) and 150mL toluene were mixed with stirring and heated to reflux for 6.5 h. After the reaction was completed, cooled to room temperature, water was added, extraction was performed with methylene chloride, the organic layer was dried over anhydrous magnesium sulfate, filtration was performed, the solvent was concentrated by distillation under reduced pressure, and recrystallization was performed with toluene to obtain compound 511 (19.72 g, yield 80%), and the purity of the solid was not less than 99.95% by HPLC. Mass spectrum m/z:821.3754 (theory: 821.3770). Theoretical element content (%) C 61 H 47 N 3 : c,89.13; h,5.76; n,5.11. Measured element content (%): c,89.17; h,5.73; n,5.10.
Synthesis example 26 Synthesis of Compound 517
According to the same manner as that of Synthesis example 3 except that a1-49 was replaced with equimolar a2-269 and b1-49 was replaced with equimolar b1-8, compound 517 (16.29 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.96%. Mass spectrum m/z:743.3320 (theory: 743.3300). Theoretical element content (%) C 55 H 41 N 3 : c,88.80; h,5.56; n,5.65. Measured element content (%): c,88.83; h,5.55; n,5.63.
Synthesis example 27 Synthesis of Compound 520
According to the same manner as that of Synthesis example 3 except that a1-49 was replaced with equimolar a1-66 and b1-49 was replaced with equimolar b1-8,e-49 with equimolar e-520, compound 520 (18.14 g) was obtained, and the purity of the solid as measured by HPLC was not less than 99.92%. Mass spectrum m/z:863.4248 (theory: 863.4239). Theoretical element content (%) C 64 H 53 N 3 : c,88.96; h,6.18; n,4.86. Equimolar ofMeasured element content (%): c,88.99; h,6.16; n,4.85.
Synthesis example 28 Synthesis of Compounds 2-67
Preparation of intermediate F-67:
under the protection of nitrogen, the raw material f-67 (120.00 mmol,38.79 g), the raw material g-67 (125.00 mmol,19.55 g) and Pd (PPh) are added into a reaction bottle in sequence 3 ) 4 (2.50mmol，2.89g)、K 2 CO 3 (240.00 mmol,33.17 g) and 360mL toluene, 120mL ethanol and 120mL water, and the mixture is stirred, and the reactant system is heated and refluxed for reaction for 3 hours; after the reaction was completed, cooled to room temperature, suction filtered to obtain a filter cake, and the filter cake was rinsed with ethanol, and finally the filter cake was purified with toluene/ethanol=4: 1 recrystallisation to give intermediate F-67 (37.05 g, 87% yield); HPLC purity is not less than 98.32%. Mass spectrum m/z:354.1162 (theory: 354.1175).
Preparation of intermediate G-67:
under the protection of nitrogen, the intermediate F-67 (100.00 mmol,35.49 g), the raw material h-67 (105.00 mmol,26.66 g) and Pd (dppf) Cl are added into a reaction bottle in sequence 2 (1.50 mmol,1.10 g), KOAc (200.00 mmol,19.63 g), 1, 4-dioxane (500 mL), stirring the mixture, heating the above reactant system to reflux for 5.5 hours, cooling to room temperature after the reaction is completed, adding 700mL of distilled water, extracting with ethyl acetate (350 mL. Times.3), and extracting the organic layer with anhydrous MgSO 4 Drying, rotary evaporation of ethyl acetate followed by recrystallisation from toluene gave intermediate G-67 (35.71G, 80% yield); HPLC purity is not less than 98.61%. Mass spectrum m/z:446.2428 (theory: 446.2417).
Preparation of intermediate H-67:
under the protection of nitrogen, the intermediate G-67 (75.00 mmol, 33.48G), the raw material i-67 (80.00 mmol, 18.07G) and Pd (dppf) Cl are added into a reaction bottle in sequence 2 (1.30mmol，0.95g)、Na 2 CO 3 (150.00 mmol,15.90 g) and 240mL toluene, 80mL ethanol, 80mL water, and stirring and mixingHeating and refluxing the reactant system for 7.5 hours; after the reaction was completed, cooled to room temperature, suction filtered to obtain a filter cake, and the filter cake was rinsed with ethanol, and finally the filter cake was purified with toluene/ethanol=8: 1 recrystallisation to give intermediate H-67 (27.23 g, 78% yield); HPLC purity is not less than 98.84%. Mass spectrum m/z:464.1085 (theory: 464.1099).
Preparation of intermediate I-67:
under the protection of nitrogen, the intermediate H-67 (55.00 mmol,25.60 g), the raw material H-67 (115.00 mmol,29.20 g) and Pd (dppf) Cl are added into a reaction bottle in sequence 2 (1.00 mmol,0.73 g), KOAc (110.00 mmol,10.80 g), 1, 4-dioxane (600 mL), stirring the mixture, and heating the reaction system to reflux for reaction for 8 hours; after the completion of the reaction, the mixture was cooled to room temperature, 900mL of distilled water was added, followed by extraction with ethyl acetate (350 mL. Times.3), and the organic layer was dried over anhydrous MgSO 4 Drying, rotary evaporation of ethyl acetate, then recrystallisation using toluene, drying gives intermediate I-67 (28.53 g, 80% yield); the HPLC purity is more than or equal to 99.56 percent. Mass spectrum m/z:648.3595 (theory: 648.3582).
Preparation of Compounds 2-67:
under the protection of nitrogen, the intermediate I-67 (35.00 mmol,22.70 g), the raw material j-67 (75.00 mmol,11.52 g) and Pd are added into a reaction bottle in sequence 2 (dba) 3 (0.60mmol，0.55g)、P(t-Bu) 3 (1.20 mmol,2.40ml of 0.5M toluene solution), K 2 CO 3 (70.00 mmol,9.67 g) and 150ml of tetrahydrofuran, the mixture was stirred, and the above-mentioned reactant system was heated under reflux for 9 hours; after the reaction, cooling to room temperature, suction filtering to obtain a filter cake, flushing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene to obtain a compound 2-67 (17.44 g, yield 79%); HPLC purity is more than or equal to 99.95%. Mass spectrum m/z:630.2320 (theory: 630.2307). Theoretical element content (%) C 45 H 30 N 2 O 2 : c,85.69; h,4.79; n,4.44. Measured element content (%): c,85.71; h,4.78; n,4.47.
Synthesis example 29 Synthesis of Compounds 2-85
Following the procedure for the preparation of synthesis example 28, F-67 was replaced with equimolar F-85 to give compound 2-85 (17.82 g, 81% yield); the HPLC purity is more than or equal to 99.97 percent. Mass spectrum m/z:628.2163 (theory: 628.2151). Theoretical element content (%) C 45 H 28 N 2 O 2 : c,85.97; h,4.49; n,4.46. Measured element content (%): c,85.95; h,4.47; n,4.47.
Synthesis example 30 Synthesis of Compounds 2-90
Following the procedure for the preparation of Synthesis example 28, substituting f-67 with equimolar f-90, compound 2-90 (17.61 g) is obtained; HPLC purity is more than or equal to 99.98%. Mass spectrum m/z:670.2283 (theory: 670.2256). Theoretical element content (%) C 47 H 30 N 2 O 3 : c,84.16; h,4.51; n,4.18. Measured element content (%): c,84.17; h,4.52; n,4.15.
Synthesis example 31 Synthesis of Compounds 2-95
Following the procedure for the preparation of synthesis example 28, f-67 was replaced with equimolar f-95 to give compound 2-95 (19.27 g, 77% yield); the HPLC purity is more than or equal to 99.97 percent. Mass spectrum m/z:714.3233 (theory: 714.3246). Theoretical element content (%) C 51 H 42 N 2 O 2 : c,85.68; h,5.92; n,3.92. Measured element content (%): c,85.67; h,5.93; n,3.91.
Synthesis example 32 Synthesis of Compounds 2-102
Following the procedure for the preparation of Synthesis example 28, substituting f-67 with equimolar f-102 and substituting j-67 with equimolar j-102, compound 2-102 (19.12 g) was obtained; HPLC purity is more than or equal to 99.96%. Mass spectrum m/z:718.2918 (theory: 718.2901). Theoretical element content (%) C 47 H 18 D 10 N 6 O 2 : c,78.53; h,5.33; n,11.69. Measured element content (%): c,78.55; h,5.38; n,11.63.
Synthesis example 33 Synthesis of Compounds 2-136
Following the procedure for the preparation of Synthesis example 28, substituting f-67 with equimolar f-136 and substituting j-67 with equimolar j-136, compound 2-136 (18.02 g) was obtained; HPLC purity is more than or equal to 99.96%. Mass spectrum m/z:714.3133 (theory: 714.3122). Theoretical element content (%) C 51 H 26 D 8 N 2 O 2 : c,85.69; h,5.92; n,3.92. Measured element content (%): c,85.66; h,5.91; n,3.95.
Synthesis example 34 Synthesis of Compounds 2-164
Following the procedure for the preparation of Synthesis example 28, substituting f-67 with equimolar f-164 and substituting j-67 with equimolar j-164 gave Compound 2-164 (21.79 g); HPLC purity is more than or equal to 99.98%. Mass spectrum m/z:914.3885 (theory: 914.3872). Theoretical element content (%) C 67 H 50 N 2 O 2 : c,87.94; h,5.51; n,3.06. Measured element content (%): c,87.91; h,5.53; n,3.08.
Synthesis example 35 Synthesis of Compounds 2-180
Following the procedure for the preparation of Synthesis example 28, substituting f-67 with equimolar f-180 and substituting j-67 with equimolar j-180, compound 2-180 (18.73 g) was obtained; the HPLC purity is more than or equal to 99.97 percent. Mass spectrum m/z:732.2756 (theory: 732.2777). Theoretical element content (%) C 53 H 36 N 2 O 2 : c,86.86; h,4.95; n,3.82. Measured element content (%): c,86.83; h,4.96; n,3.81.
Synthesis example 36 Synthesis of Compounds 2-258
Following the procedure for the preparation of Synthesis example 28, substituting f-67 with equimolar f-180 and g-67 with equimolar g-258, compound 2-258 (15.68 g) was obtained; HPLC purity is more than or equal to 99.95%. Mass spectrum m/z:581.2123 (theory: 581.2103). Theoretical element content (%) C 40 H 27 N 3 O 2 : c,82.60; h,4.68; n,7.22. Measured element content (%): c,82.63; h,4.66; n,7.23.
Synthesis example 37 Synthesis of Compounds 2-269
Following the procedure for the preparation of Synthesis example 28 substituting f-67 with equimolar f-269 and g-67 with equimolar g-269, compound 2-269 (20.90 g) was obtained; the HPLC purity is more than or equal to 99.97 percent. Mass spectrum m/z:755.2585 (theory: 755.2573). Theoretical element content (%) C 54 H 33 N 3 O 2 : c,85.81; h,4.40; n,5.56. Measured element content (%): c,85.85; h,4.41; n,5.53.
Synthesis example 38 Synthesis of Compounds 2-297
Following the procedure for the preparation of synthetic example 28 substituting f-67 with equimolar f-297 and g-67 with equimolar g-297, compound 2-297 (19.76 g, 75% yield) was obtained; HPLC purity is more than or equal to 99.96%. Mass spectrum m/z:752.2473 (theory: 752.2464). Theoretical element content (%) C 55 H 32 N 2 O 2 : c,87.74; h,4.28; n,3.72. Measured element content (%): c,87.77; h,4.23; n,3.71.
Synthesis example 39 Synthesis of Compounds 2-308
Following the procedure for the preparation of Synthesis example 28, substituting f-67 with equimolar f-180 and g-67 with equimolar g-308, compound 2-308 (17.01 g) was obtained; the HPLC purity is more than or equal to 99.97 percent. Mass spectrum m/z:656.2423 (theory: 656.2464). Theoretical element content (%) C 47 H 32 N 2 O 2 : c,85.95; h,4.91; n,4.27. Measured element content (%): c,85.92; h,4.92; n,4.29.
Synthesis example 40 Synthesis of Compounds 2-345
Following the procedure for the preparation of Synthesis example 28, substituting f-67 with equimolar f-180 and g-67 with equimolar g-345, compound 2-345 (19.02 g) was obtained; HPLC purity is more than or equal to 99.98%. Mass spectrum m/z:696.2788 (theory: 696.2777). Theoretical element content (%) C 50 H 36 N 2 O 2 : c,86.18; h,5.21; n,4.02. Measured element content (%): c,86.23; h,5.23; n,4.00.
Synthesis example 41 Synthesis of Compounds 2-355
Following the procedure for the preparation of Synthesis example 28, substituting f-67 with equimolar f-180 and g-67 with equimolar g-355, compound 2-355 (16.90 g) was obtained; the HPLC purity is more than or equal to 99.97 percent. Mass spectrum m/z:670.2244 (theory: 670.2256). Theoretical element content (%) C 47 H 30 N 2 O 3 : c,84.16; h,4.51; n,4.18. Measured element content (%): c,84.18; h,4.53; n,4.16.
Synthesis example 42 Synthesis of Compounds 2-360
Preparation of intermediate F-360:
under the protection of nitrogen, raw material f-360 (260.00 mmol,94.98 g), raw material g-67 (270.00 mmol,42.22 g) and Pd (PPh) are added into a reaction bottle in sequence 3 ) 4 (5.00mmol，5.78g)、K 2 CO 3 (520.00 mmol,71.87 g) and 720mL toluene, 240mL ethanol and 240mL water, and the mixture was stirred, and the above reactant system was heated under reflux for 4 hours; after the reaction was completed, cooled to room temperature, suction filtered to obtain a filter cake, and the filter cake was rinsed with ethanol, and finally the filter cake was purified with toluene/ethanol=5: 1 recrystallisation to give intermediate F-360 (90.82 g, 88% yield); HPLC purity is not less than 98.14%. Mass spectrum m/z:396.1658 (theory: 396.1645).
Preparation of intermediate G-360:
under the protection of nitrogen, the intermediate F-360 (210.00 mmol,83.36 g), the raw material h-67 (215.00 mmol,54.60 g) and Pd (dppf) Cl are added into a reaction bottle in sequence 2 (4.00 mmol,2.93 g), KOAc (420.00 mmol,41.22 g), 1, 4-dioxane (800 mL), stirring the mixture, heating the above reactant system to reflux for 6 hours, cooling to room temperature after the reaction, adding 900mL of distilled water, extracting with ethyl acetate (500 mL. Times.3), and extracting the organic layer with anhydrous MgSO 4 Drying, rotary evaporation of ethyl acetate followed by recrystallisation from toluene afforded intermediate G-360 (84.12G, 82% yield); HPLC purity is not less than 98.46%. Mass spectrum m/z:488.2878 (theory: 488.2887).
Preparation of intermediate H-360:
under the protection of nitrogen, the intermediate G-360 (160.00 mmol, 78.16G), the raw material i-360 (165.00 mmol, 52.36G) and Pd (dppf) Cl are added into a reaction bottle in sequence 2 (3.50mmol，2.56g)、Na 2 CO 3 (320.00 mmol,33.92 g) and 480mL toluene, 160mL ethanol and 160mL water, and the mixture was stirred, and the reaction system was heated under reflux for 8 hours; after the reaction was completed, cooled to room temperature, suction filtered to obtain a filter cake, and the filter cake was rinsed with ethanol, and finally the filter cake was purified with toluene/ethanol=8: 1 recrystallisation to give intermediate H-360 (69.77 g, 79% yield); HPLC purity is not less than 98.78%. Mass spectrum m/z:550.1074 (theory: 550.1063).
Preparation of intermediate I-360:
under the protection of nitrogen, the intermediate H-360 (120.00 mmol,66.23 g), the raw material H-67 (250.00 mmol,63.49 g) and Pd (dppf) Cl are added into a reaction bottle in sequence 2 (2.00 mmol,1.46 g), KOAc (240.00 mmol,23.55 g), 1, 4-dioxane (800 mL), stirring the mixture, and heating the reaction system to reflux for reaction for 9 hours; after the completion of the reaction, 1000mL of distilled water was added after cooling to room temperature, followed by extraction with ethyl acetate (350 mL. Times.3), and the organic layer was dried over anhydrous MgSO 4 Drying, rotary evaporation of ethyl acetate, then recrystallisation using toluene, drying gives intermediate I-360 (57.51 g, 80% yield); HPLC purity is more than or equal to 99.13%. Mass spectrum m/z:598.2823 (theory: 598.2810).
Preparation of intermediate J-360:
under the protection of nitrogen, the intermediate I-360 (80.00 mmol,47.93 g), the raw material j-67 (85.00 mmol,13.05 g) and Pd are added into a reaction bottle in sequence 2 (dba) 3 (1.60mmol，1.47g)、P(t-Bu) 3 (3.20 mmol,6.40ml of 0.5M toluene solution), K 2 CO 3 (160.00 mmol,22.11 g) and 300ml of tetrahydrofuran, and the mixture was stirred, and the above-mentioned reactant system was heated under reflux for 9 hours; after the reaction is finished, coolCooling to room temperature, filtering to obtain a filter cake, flushing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene to obtain an intermediate J-360 (36.35 g, yield 77%); HPLC purity is more than or equal to 99.47%. Mass spectrum m/z:589.2185 (theory: 589.2172).
Preparation of intermediate K-360:
intermediate J-360 (60.00 mmol,35.41 g), starting material h-67 (65.00 mmol,16.51 g), pd (dppf) Cl were added sequentially to the reaction flask under nitrogen 2 (1.00 mmol,0.73 g), KOAc (120.00 mmol,11.78 g), 1, 4-dioxane (600 mL), stirring the mixture, heating the above reactant system to reflux for 5.5 hours, cooling to room temperature after the reaction is completed, adding 700mL of distilled water, extracting with ethyl acetate (350 mL. Times.3), and extracting the organic layer with anhydrous MgSO 4 Drying, rotary evaporation of ethyl acetate followed by recrystallisation from toluene afforded intermediate K-360 (30.27 g, 74% yield); HPLC purity is more than or equal to 99.78%. Mass spectrum m/z:681.3423 (theory: 681.3414).
Preparation of Compounds 2-360:
following the procedure for the preparation of synthetic example 28, substituting equimolar K-360 for I-67 and equimolar j-360 for j-67 gave compound 2-360 (19.69 g, 75% yield); the HPLC purity is more than or equal to 99.97 percent. Mass spectrum m/z:749.3051 (theory: 749.3042). Theoretical element content (%) C 53 H 39 N 3 O 2 : c,84.89; h,5.24; n,5.60. Measured element content (%): c,84.91; h,5.23; n,5.61.
Synthesis example 43 Synthesis of Compounds 2-362
Following the procedure for the preparation of Synthesis example 28, substituting f-67 with equimolar f-269, substituting g-67 with equimolar g-632, substituting j-67 with equimolar j-362 gave Compound 2-362 (21.40 g); HPLC purity is more than or equal to 99.98%. Mass spectrum m/z:860.3351 (theory: 860.3341). Theoretical element content (%) C 63 H 36 D 4 N 2 O 2 ：C,87.88；H,5.15, a step of; n,3.25. Measured element content (%): c,87.85; h,5.18; n,3.23. Synthesis example 44]Synthesis of Compounds 2-409
Following the procedure for the preparation of Synthesis example 28, substituting f-67 with equimolar f-409, substituting g-67 with equimolar g-409 and substituting j-67 with equimolar j-409, compound 2-409 (20.82 g) was obtained; HPLC purity is more than or equal to 99.96%. Mass spectrum m/z:792.2388 (theory: 792.2381). Theoretical element content (%) C 53 H 36 N 4 S 2 : c,80.27; h,4.58; n,7.07. Measured element content (%): c,80.28; h,4.59; n,7.03.
Synthesis example 45 Synthesis of Compounds 2-486
Following the procedure for the preparation of synthetic example 28, substituting f-67 with equimolar f-486, g-67 with equimolar g-486, and j-67 with equimolar j-486 gave compound 2-486 (21.97 g, 68% yield); the HPLC purity is more than or equal to 99.97 percent. Mass spectrum m/z:922.4043 (theory: 922.4035). Theoretical element content (%) C 68 H 50 N 4 : c,88.47; h,5.46; n,6.07. Measured element content (%): c,88.45; h,5.47; n,6.08.
Red organic luminescent device (hole transport layer)
Comparative examples 1-2 device preparation examples:
comparative example 1: the organic light emitting device is prepared by utilizing a vacuum thermal evaporation method. The experimental steps are as follows: the ITO substrate is put in distilled water for 3 times, washed by ultrasonic waves for 15 minutes, washed by ultrasonic waves sequentially by solvents such as isopropanol, acetone, methanol and the like after the distilled water is washed, dried and dried at 120 ℃, and sent into an evaporator.
Coating the prepared ITO transparent electrode with a layer-by-layer vacuum evaporation methodVapor deposition hole injection layer HI/60nm, vapor deposition hole transport layer HT-1/80nm, vapor deposition main body H-1: h-2: ir doped (piq) 2 acac (mass ratio 49%:49%:2% mixture)/30 nm, then evaporating the electron transport layer Alq 3 The doping ratio of Liq (1:1)/28 nm, liF/1nm of the electron injection layer and Al/120nm of the cathode. And sealing the device in a glove box, thereby preparing an organic light emitting device. After the organic light-emitting device is manufactured according to the steps, the photoelectric property of the device is measured, and the molecular structural formula of the related material is shown as follows:
comparative example 2: the organic light emitting device of comparative example 2 was manufactured in the same manner as comparative example 1, except that the hole transport layer material HT-1 in comparative example 1 was replaced with HT-2.
Application examples 1 to 27
Application examples 1-27: the hole transport layer material HT-1 of the organic light emitting device was changed to the compound 8, 22, 49, 66, 69, 85, 175, 232, 242, 246, 259, 269, 278, 306, 317, 343, 351, 367, 413, 421, 502, 504, 506, 507, 511, 517, 520 of the present invention in this order, and the other steps were the same as comparative example 1.
Test software, a computer, a K2400 digital source list manufactured by Keithley corporation, U.S. and a PR788 spectral scanning luminance meter manufactured by Photo Research corporation, U.S. were combined into a single integrated IVL test system to test the luminous efficiency of an organic light emitting device. Life testing an M6000 OLED life test system from McScience was used. The environment tested was atmospheric and the temperature was room temperature. The results of the light emission characteristics test of the obtained organic light emitting device are shown in table 1. Table 1 shows the results of the light emitting characteristics test of the light emitting devices prepared with the compounds prepared in the examples of the present invention and the comparative substances.
TABLE 1 test of light emitting characteristics of light emitting device
Note that: t97 means that the current density is 10mA/cm 2 In the case, the time taken for the device brightness to decay to 97%;
as can be seen from the results of Table 1, the triamine derivatives of the present invention are applied to organic light emitting devices, and as hole transport layer materials, the device performance is improved compared with comparative examples 1-2, and the advantages of high light emitting efficiency and long service life are exhibited, particularly, the compound of the present invention has high glass transition temperature and prolonged service life.
Comparative examples 3-17 device preparation examples:
Comparative example 3: the organic light emitting device is prepared by utilizing a vacuum thermal evaporation method. The experimental steps are as follows: the ITO substrate is put in distilled water for 3 times, washed by ultrasonic waves for 15 minutes, washed by ultrasonic waves sequentially by solvents such as isopropanol, acetone, methanol and the like after the distilled water is washed, dried and dried at 120 ℃, and sent into an evaporator.
Evaporating a hole injection layer HI/55nm, an evaporating hole transmission layer HT-1/80nm and an evaporating main body H-1 on the prepared ITO transparent electrode in a layer-by-layer vacuum evaporation mode: h-2: ir doped (ppy) 2 acac (mass ratio 46%:46%:8% mixture)/30 nm, then evaporating hole blocking layer compound 2-67, evaporating electron transport layer Alq 3 The doping ratio of Liq (1:1) to 28nm, liF/1nm of the electron injection layer and Al/125nm of the cathode. And sealing the device in a glove box, thereby preparing an organic light emitting device. After the organic light-emitting device is manufactured according to the steps, the photoelectric property of the device is measured, and the molecular structural formula of the related material is shown as follows:
comparative examples 4-6: the organic light emitting devices of comparative examples 4 to 6 were manufactured in the same manner as comparative example 3, except that the hole blocking layer compounds 2 to 67 in comparative example 3 were replaced with 2 to 85, 2 to 258, and 2 to 308.
Comparative examples 7-9: the organic light-emitting devices of comparative examples 7 to 9 were fabricated in the same manner as in comparative example 3, except that the hole transport layer HT-1 in comparative example 3 was replaced with the inventive compounds 49, 66, 242, and the hole blocking layer compounds 2 to 67 were replaced with HB-1, HB-2, HB-3.
Comparative examples 10 to 18: the organic light-emitting devices of comparative examples 10 to 18 were fabricated in the same manner as in comparative example 3, except that the hole transport layer HT-1 in comparative example 3 was replaced with the inventive compounds 242, 66, 259, 269, 517, 49, 69, 232, 413 and the hole blocking layer compound HB-1 was replaced with nothing.
Application examples 28 to 53: the hole transport layer material HT-1 of the organic light emitting device was changed to the inventive compound 8, 22, 49, 66, 69, 85, 175, 232, 242, 246, 259, 269, 278, 306, 317, 343, 351, 367, 413, 421, 502, 504, 506, 507, 511, 517 in this order, the hole blocking layer compound HB-1 was changed to the inventive compound 2-67, 2-85, 2-90, 2-95, 2-102, 2-136, 2-164, 2-180, 2-258, 2-269, 2-297, 2-308, 2-345, 2-355, 2-360, 2-362, 2-409, 2-486, 2-67, 2-85, 2-95, 2-164, 2-180, 2-258, 2-297, 2-308, 2-345, 2-409, 2-486, and the other steps were the same as comparative example 3.
TABLE 2 test of light emitting characteristics of light emitting device
As can be seen from the results of Table 2, the organic light emitting device of the present invention exhibits the advantages of high luminous efficiency and long service life as compared with comparative examples 3 to 18, and is an organic light emitting device having good performance. The combination of the specific hole transport material and the specific hole blocking material of the invention shows the synergistic effect of the hole transport layer and the hole blocking layer, and the synergistic effect of the two makes the performance of the organic light emitting device break through the limit of the conventional organic light emitting device, and has the advantages of high light emitting efficiency and long service life.
It should be noted that while the invention has been particularly described with reference to individual embodiments, those skilled in the art may make various modifications in form or detail without departing from the principles of the invention, which modifications are also within the scope of the invention.
Claims (10)
1. A triamine derivative, which is characterized in that the molecular structure is shown as a formula I:
wherein the R is 1 、R 2 At least one of which is selected from substituted or unsubstituted C1-C10 alkyl, R 3 A substituent selected from hydrogen, cyano or halogen, and the substituent in the 'substituted or unsubstituted' is selected from one or more of methyl, ethyl, isopropyl and tert-butyl;
The Ar is as follows 1 A substituted or unsubstituted aryl group of 10 to 25 carbon atoms, wherein the substituent in the "substituted or unsubstituted" group is selected from one or more of cyano, halogen, methyl, ethyl, isopropyl and tert-butyl;
the Ar is as follows 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from the group represented by formula a:
the R is m The same or different alkyl groups selected from hydrogen, cyano, halogen, substituted or unsubstituted C1-C10One of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, or optionally two adjacent R groups m The groups may be bonded to form a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring, wherein the substituents in "substituted or unsubstituted" are selected from one or more of cyano, halogen, methyl, ethyl, isopropyl, tert-butyl;
the m is 1 Selected from 0, 1, 2, 3, 4 or 5;
the L is 1 、L 2 、L 3 、L 4 、L 5 、L 6 Independently selected from one of single bond, substituted or unsubstituted C6-C25 arylene, wherein the substituent in the "substituted or unsubstituted" is selected from one or more of cyano, halogen, methyl, ethyl, isopropyl and tert-butyl.
2. The triamine derivative according to claim 1, characterized in that the R 1 、R 2 At least one of which is selected from the group consisting of substituted or unsubstituted: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, wherein the substituents in "substituted or unsubstituted" are selected from methyl, ethyl, isopropyl, tert-butyl.
3. The triamine derivative according to claim 1, wherein the Ar 1 Any one selected from the following groups:
the R is r The same or different R is selected from one of hydrogen, cyano, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, or two adjacent R r The groups may be bonded to form substituted or unsubstitutedA benzene ring, a substituted or unsubstituted naphthalene ring, wherein the substituents in the "substituted or unsubstituted" are selected from one or more of cyano, halogen, methyl, ethyl, isopropyl, tert-butyl;
the r is 1 Selected from 0, 1, 2, 3, 4 or 5; the r is 2 Selected from 0, 1, 2, 3 or 4; the r is 4 Selected from 0, 1, 2, 3, 4, 5, 6 or 7.
4. The triamine derivative according to claim 1, wherein the Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from any one of the following groups:
the R is m One selected from hydrogen, cyano, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, naphthyl, biphenyl, terphenyl, or optionally two adjacent R m The groups may be bonded together to form a substituted or unsubstituted benzene ring;
wherein said R is m Can also be R mm Substituted, R mm One or more selected from hydrogen, cyano, halogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, anthryl, phenanthryl, triphenylene, and in the case of being substituted with a plurality of substituents, the plurality of substituents may be the same or different from each other;
the m is 1 Selected from 0, 1, 2, 3, 4 or 5; the m is 2 Selected from 0, 1, 2, 3 or 4; the m is 3 Selected from 0, 1, 2 or 3; the m is 4 Selected from 0, 1, 2, 3, 4, 5, 6 or 7; the m is 7 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.
5. The triamine derivative according to claim 1, wherein the Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from any one of the following groups:
the R is m Identical to or different from each other, selected from hydrogen or one of the following substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, biphenyl, terphenyl, naphthyl; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, phenyl, biphenyl, naphthyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same or different from each other;
The m is 1 Selected from 0, 1, 2, 3, 4 or 5; the m is 2 Selected from 0, 1, 2, 3 or 4; the m is 3 Selected from 0, 1, 2 or 3; the m is 4 Selected from 0, 1, 2, 3, 4, 5, 6 or 7; the m is 5 Selected from 0, 1 or 2; the m is 6 Selected from 0, 1, 2, 3, 4, 5 or 6; the m is 7 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.
6. The triamine derivative according to claim 1, characterized in that the L 1 、L 2 、L 3 、L 4 、L 5 、L 6 Independently selected from a single bond or one of the following groups:
the R is n Any one selected from hydrogen, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C25 aryl; said n 1 Selected from 0, 1, 2, 3 or 4; said n 2 Selected from 0, 1, 2, 3, 4, 5 or 6.
7. The triamine derivative according to claim 1, wherein the triamine derivative represented by the formula i is selected from any one of the chemical structures shown below:
8. an organic light-emitting device comprising an anode, a cathode, and an organic layer located between the anode and the cathode or outside one or more of the anode and the cathode, wherein the organic layer comprises any one or a combination of at least two of the triamine derivatives according to any one of claims 1 to 7.
9. An organic light-emitting device according to claim 8, wherein the organic layer comprises a hole-transporting region, a light-emitting layer, an electron-transporting region, and a capping layer, and wherein at least one of the hole-transporting region, the light-emitting layer, and the capping layer comprises any one or a combination of at least two of the triamine derivatives according to any one of claims 1 to 7.
10. An organic light-emitting device according to claim 9, wherein the electron transport region comprises a heterocyclic compound of formula ii:
the Arb and Arc are the same or different and are selected from structures shown in a formula b,
z is selected from any one of O, S or N (Ry); the Ry is selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
the Y is the same or different and is selected from C (Rx) or N; the Rx is the same or different and is selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or two adjacent Rx are connected to form a substituted or unsubstituted ring;
The R is b 、R c Independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, fused ring group of substituted or unsubstituted C6-C30 aromatic ring and C3-C30 aliphatic ring, substituted or unsubstituted C2-C30 heteroaryl, or R b 、R c Can be combined with each other to form a substituted or unsubstituted spiro ring; r is R b 、R c Any one of which can be directly bonded to the bridging La;
the R is 0 Selected from hydrogen, deuterium, cyanoAny one of halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; the a is selected from 0, 1, 2 or 3;
the R is a 、R t Independently selected from any one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C3-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; or two adjacent R a May be linked to form a substituted or unsubstituted aromatic or aliphatic ring; or two adjacent R t May be linked to form a substituted or unsubstituted aromatic or aliphatic ring;
the a 1 Selected from 0, 1, 2, 3 or 4; the a 2 Selected from 0, 1, 2, 3 or 4; said t is selected from 0, 1, 2, 3 or 4;
the L is a 、L b 、L c The same or different one selected from single bond, substituted or unsubstituted arylene of C6-C30, substituted or unsubstituted heteroarylene of C2-C30, substituted or unsubstituted alicyclic of C3-C10 and condensed ring group of aromatic ring of C6-C25.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310125475.2A CN116023275A (en) | 2023-02-16 | 2023-02-16 | Triamine derivative and organic light-emitting device thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310125475.2A CN116023275A (en) | 2023-02-16 | 2023-02-16 | Triamine derivative and organic light-emitting device thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116023275A true CN116023275A (en) | 2023-04-28 |
Family
ID=86079536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310125475.2A Pending CN116023275A (en) | 2023-02-16 | 2023-02-16 | Triamine derivative and organic light-emitting device thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116023275A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116891449A (en) * | 2023-07-28 | 2023-10-17 | 长春海谱润斯科技股份有限公司 | Triamine compound and organic electroluminescent device thereof |
| CN116903561A (en) * | 2023-07-28 | 2023-10-20 | 长春海谱润斯科技股份有限公司 | Triamine derivative and organic electroluminescent device thereof |
-
2023
- 2023-02-16 CN CN202310125475.2A patent/CN116023275A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116891449A (en) * | 2023-07-28 | 2023-10-17 | 长春海谱润斯科技股份有限公司 | Triamine compound and organic electroluminescent device thereof |
| CN116903561A (en) * | 2023-07-28 | 2023-10-20 | 长春海谱润斯科技股份有限公司 | Triamine derivative and organic electroluminescent device thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113620818B (en) | Triarylamine compound containing condensed rings and organic light-emitting device thereof | |
| CN113443998B (en) | Triarylamine organic compound and organic light-emitting device thereof | |
| CN113527181A (en) | Nitrogen-containing heterocyclic organic compound and organic light-emitting device thereof | |
| CN114573462B (en) | Triamine compound and organic light-emitting device thereof | |
| CN113683630B (en) | Nitrogen-containing heterocyclic derivative and organic electroluminescent device thereof | |
| CN116023275A (en) | Triamine derivative and organic light-emitting device thereof | |
| CN114634419A (en) | Aromatic amine compound and organic electroluminescent device thereof | |
| CN115057849B (en) | Triarylamine organic compound and organic light-emitting device thereof | |
| CN115057838B (en) | Aromatic amine organic compound and organic light-emitting device thereof | |
| CN114621102B (en) | Aromatic amine derivative and organic electroluminescent device thereof | |
| CN116261347A (en) | Organic electroluminescent device | |
| CN114621181B (en) | Star-shaped tetramine derivative and organic electroluminescent device thereof | |
| CN116375588A (en) | Diamine compound and organic light-emitting device thereof | |
| CN116283862A (en) | Star-shaped triarylamine derivative and organic electroluminescent device thereof | |
| CN115385802A (en) | Organic electroluminescent device | |
| CN113831332A (en) | Nitrogen-containing heterocyclic derivative and application thereof in organic electroluminescent device | |
| CN113845512A (en) | Compound containing heterocycle and organic electroluminescent device thereof | |
| CN114944459B (en) | Organic electroluminescent device | |
| CN114899344B (en) | Organic electroluminescent device | |
| CN116947652A (en) | Diamine derivative and organic electroluminescent device thereof | |
| CN117082886A (en) | Organic electroluminescent device | |
| CN117377338A (en) | Organic electroluminescent device | |
| CN114944459A (en) | Organic electroluminescent device | |
| CN115819410A (en) | Heterocyclic derivative and organic light-emitting device thereof | |
| CN116217410A (en) | Diamine derivative and organic electroluminescent device thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |