CN111635384B - Arylamine organic compound and organic light-emitting device thereof - Google Patents

Arylamine organic compound and organic light-emitting device thereof Download PDF

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CN111635384B
CN111635384B CN202010635112.XA CN202010635112A CN111635384B CN 111635384 B CN111635384 B CN 111635384B CN 202010635112 A CN202010635112 A CN 202010635112A CN 111635384 B CN111635384 B CN 111635384B
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arylamine
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刘喜庆
韩春雪
苗玉鹤
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Changchun Hyperions Technology Co Ltd
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Abstract

The invention provides an arylamine organic compound and an organic light-emitting device thereof, and relates to the technical field of organic photoelectric materials. The arylamine organic compound has a special rigid condensed ring structure, can relatively limit the movement of the whole group and endows the group with strong photoelectric performance, so that the arylamine organic compound has good thermal stability, can make the compound more stable, can be used as a hole transport layer material, and has the advantages of good luminous efficiency and low driving voltage. The arylamine organic compound has good film forming property, simple synthesis and easy operation, and can be widely applied to the fields of panel display, lighting sources, organic solar cells, organic photoreceptors or organic thin film transistors and the like.

Description

Arylamine organic compound and organic light-emitting device thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to an arylamine organic compound and an organic light-emitting device thereof.
Background
The OLED is called an organic light emitting diode or an organic light emitting display screen, and is a new application technology in the display field, and has the characteristics of self-luminescence, wide viewing angle, full curing, full colorization, high reaction speed, high brightness, low driving voltage, thin thickness, light weight, capability of manufacturing large-size and curved panels, and the like.
The OLED is very suitable for being applied to a panel with a medium or small size, and is widely accepted in the fields of mobile phones, wearable products, VR and the like at present. In addition, since the OLED is an all-solid-state and non-vacuum device, the OLED has the characteristics of shock resistance, low temperature resistance and the like, and has important application in the military aspect. Due to rapid development of industries such as downstream market smart phones, tablet computers and vehicle-mounted sound equipment, rapid growth of the OLED display screen industry is driven, and market scale in the future cannot be estimated.
In the OLED device, the carrier transport material is classified into an Electron Transport Material (ETM) and a Hole Transport Material (HTM) according to the property of charge transport. The hole transport layer basically has the functions of improving the transport efficiency of holes in the device and effectively blocking electrons in the light-emitting layer to realize the maximum recombination of current carriers; meanwhile, the energy barrier of the holes in the injection process is reduced, and the injection efficiency of the holes is improved, so that the brightness, the efficiency and the service life of the device are improved. The hole transport material should have the following properties: a) the hole mobility is good, so that good hole transmission performance is guaranteed; b) capable of forming a uniform amorphous film free of pinholes; c) the formed amorphous film has good thermal stability; d) have suitable HOMO orbital levels to ensure efficient injection and transport of holes between the electrode/organic layer and the organic layer/organic layer interface.
Since the device is operating to generate joule heat, this heat often causes recrystallization of the material. Crystallization can destroy the uniformity of the film and also destroy the good interfacial contact between the hole transport layer and the anode and the organic layer, resulting in reduced efficiency and lifetime of the device. And the injection of holes and electrons is unbalanced due to the low mobility of the holes, and the holes and the electrons cannot be effectively combined in the light-emitting layer, so that the light-emitting efficiency of the organic electroluminescent device is reduced. Therefore, the research on the organic hole transport material focuses on improving the thermal stability and hole mobility of the material.
In general, in the future, the OLED is developed to be a white light device and a full color display device with high efficiency, long lifetime and low cost, but the industrialization process of the technology still faces many key problems, and how to design a material with better performance for adjustment is a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide an arylamine organic compound and an organic light-emitting device thereof.
The invention provides an arylamine organic compound which is used as a main component of a hole transport layer in an organic light-emitting device and solves the problems, and the molecular structural general formula of the arylamine organic compound is shown as the following formula I:
Figure BDA0002569338510000021
wherein, L is selected from one of single bond, substituted or unsubstituted C6-C25 arylene, substituted or unsubstituted C2-C20 heteroarylene;
Ar1、Ar2、Ar3、Ar4at least one of them is a group represented by the following formula II, and the others are independently selected from one of substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl:
Figure BDA0002569338510000022
wherein X is selected from O, S, Se, N-Ra、C-RbRcOne of (1), RaOne selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C2-C20 heteroaryl; rb、RcThe same or different one selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl, or Rb、RcBonded together to form a ring structure;
the ring A is selected from one of no, benzene ring and naphthalene ring;
R1one selected from H, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C2-C20 heteroaryl;
when ring A is selected from null, p is selected from an integer from 0 to 2; when ring A is selected from a benzene ring, p is selected from an integer of 0 to 4; when ring A is selected from naphthalene rings, p is selected from an integer of 0 to 6;
Lnone selected from single bond, substituted or unsubstituted C6-C25 arylene, and substituted or unsubstituted C2-C20 heteroarylene.
Preferably, the formula II is selected from one of the groups shown in formulas II-a to II-e below:
Figure BDA0002569338510000023
preferably, Ar is1One selected from the group shown below:
Figure BDA0002569338510000024
wherein R is1Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, trimethyleneOne of phenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl and dibenzofuranyl;
Lnone selected from single bond, phenylene, naphthylene, biphenylene and tolylene;
Raone selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl, dibenzofuranyl.
Preferably, Ar is2、Ar3、Ar4Independently selected from one of the groups shown:
Figure BDA0002569338510000031
one of propyl, n-butyl, isopropyl, tert-butyl, phenyl, tolyl, biphenyl and naphthyl;
Rpone selected from deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, acridine, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, pyrenyl, indolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl;
q is 0,1 or 2;
L1one selected from the group consisting of formulas (1) to (14):
Figure BDA0002569338510000032
the invention also provides an organic light-emitting device which comprises a cathode, an anode and one or more organic layers arranged between the two electrodes and outside the two electrodes, wherein the organic layer arranged between the cathode and the anode comprises a hole injection layer, a hole transport layer and at least one of an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer; the organic layer disposed outside the cathode and the anode includes a capping layer; the organic layer contains any one or a combination of at least two of the aromatic amine organic compounds.
Preferably, the organic layer of the present invention includes a hole transport layer, and the hole transport layer contains any one or a combination of at least two of the arylamine organic compounds of the present invention.
The invention has the beneficial effects that:
the invention provides an arylamine organic compound and an organic light-emitting device thereof, wherein tetramethyl spiroindane is used as a bridging group, an arylamine structure is introduced and is connected with dibenzothiophene group, dibenzofuran group or carbazolyl and the like as substituent groups, so that the electron donating capability of the compound is further enhanced, the compound has good hole transport performance, and the compound is a good hole transport material; the arylamine organic compound has a special rigid condensed ring structure, can relatively limit the movement of the whole group, can obviously reduce the aggregation state fluorescence quenching phenomenon of the material, and improves the stability of the compound.
The arylamine organic compound is applied to an organic light-emitting device, and the organic light-emitting device prepared by using the arylamine organic compound as a hole transport layer material has the advantages of high light-emitting efficiency and low driving voltage.
Drawings
FIG. 1 is a drawing showing Compound 1 of the present invention1A HNMR map; FIG. 2 is a drawing showing Compound 9 of the present invention1A HNMR map;
FIG. 3 is a drawing showing a preparation of compound 30 of the present invention1A HNMR map; FIG. 4 shows Compound 41 of the present invention1A HNMR map;
FIG. 5 is a drawing showing a scheme of preparing a compound 63 of the present invention1A HNMR map; FIG. 6 shows Compound 86 of the present invention1A HNMR map;
FIG. 7 is a drawing showing a scheme of Compound 130 of the present invention1HNMR picture(ii) a FIG. 8 is a drawing of compound 189 of the present invention1HNMR map.
Detailed Description
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection of the present invention.
The alkyl group in the present invention refers to a hydrocarbon group obtained by dropping one hydrogen atom from an alkane molecule, and it may be a straight-chain or branched 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 methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl and the like, but is not limited thereto; the branched alkyl group includes, but is not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, the isomeric form of n-pentyl, the isomeric form of n-hexyl, the isomeric form of n-heptyl, the isomeric form of n-octyl, the isomeric form of n-nonyl, the isomeric form of n-decyl, and the like. The above 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 and a tert-butyl group.
The aryl group in the present invention refers to a general term of monovalent group remaining after one hydrogen atom is removed from an aromatic nucleus carbon of an aromatic compound molecule, and may be monocyclic aryl group, polycyclic aryl group or condensed ring aryl group, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 14 carbon atoms. The monocyclic aryl group means an aryl group having only one aromatic ring in the molecule, for example, phenyl group and the like, but is not limited thereto; the polycyclic aromatic group means an aromatic group having two or more independent aromatic rings in the molecule, for example, biphenyl group, terphenyl group and the like, but is not limited thereto; the fused ring aryl group refers to an aryl group in which two or more aromatic rings are contained in a molecule and are fused together by sharing two adjacent carbon atoms, and examples thereof include, but are not limited to, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylene, fluoranthenyl, spirobifluorenyl, and the like. The above 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 triphenylene group, or a spirobifluorenyl group.
The heteroaryl group in the present invention refers to a general term of a group obtained by replacing one or more aromatic nucleus carbon atoms in an aryl group with a heteroatom, including but not limited to oxygen, sulfur, nitrogen or phosphorus atom, preferably having 1 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 3 to 12 carbon atoms, wherein the attachment site of the heteroaryl group may be located on a ring-forming carbon atom or a ring-forming nitrogen atom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group or a fused ring heteroaryl group. The monocyclic heteroaryl group includes pyridyl, pyrimidyl, triazinyl, furyl, thienyl, pyrrolyl, imidazolyl and the like, but is not limited thereto; the polycyclic heteroaryl group includes bipyridyl, phenylpyridyl, and the like, but is not limited thereto; the fused ring heteroaryl group includes quinolyl, isoquinolyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, benzocarbazolyl, acridinyl, 9, 10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiyl and the like, but is not limited thereto. 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 dibenzofuryl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group or a phenoxathiyl group.
The arylene group in the present invention refers to a general term of a divalent group remaining after two hydrogen atoms are removed from an aromatic core carbon of an aromatic compound molecule, and may be a monocyclic arylene group, a polycyclic arylene group or a condensed ring arylene group, and preferably has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 14 carbon atoms. The monocyclic arylene group includes phenylene group and the like, but is not limited thereto; the polycyclic arylene group includes, but is not limited to, biphenylene, terphenylene, and the like; the condensed ring arylene group includes naphthylene, anthrylene, phenanthrylene, fluorenylene, pyrenylene, triphenylene, fluoranthenylene, phenylfluorenylene, and the like, but is not limited thereto. The arylene group is preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a fluorenylene group, or a phenylfluorenylene group.
Heteroarylene as used herein refers to the generic term for groups in which one or more of the aromatic core carbons in the arylene group is replaced with a heteroatom, including, but not limited to, oxygen, sulfur, nitrogen, or phosphorus atoms. Preferably having 1 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 3 to 12 carbon atoms, and the linking site of the heteroarylene group may be located on a ring-forming carbon atom or 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 a pyridylene group, a pyrimidylene group, a triazinylene group, a furanylene group, a thiophenylene group and the like, but is not limited thereto; the polycyclic heteroarylene group includes bipyridyl idene, phenylpyridyl, etc., but is not limited thereto; the fused ring heteroarylene group includes, but is not limited to, a quinolylene group, an isoquinolylene group, an indolyl group, a benzothiophene group, a benzofuranylene group, a benzoxazolyl group, a benzimidazolylene group, a benzothiazolyl group, a dibenzofuranylene group, a dibenzothiophenylene group, a carbazolyl group, a benzocarbazolyl group, an acridinylene group, a 9, 10-dihydroacridine group, a phenoxazinyl group, a phenothiazinylene group, a phenoxathiin group and the like. The heteroaryl group is preferably a pyridylene group, pyrimidylene group, thienylene group, furylene group, benzothienylene group, benzofuranylene group, benzoxazolyl group, benzimidazolylene group, benzothiazolyl group, dibenzofuranylene group, dibenzothiophenylene group, dibenzofuranylene group, carbazolyl group, acridinylene group, phenoxazinyl group, phenothiazinylene group or phenoxathiin group.
The substituted alkyl, substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene as described herein means mono-or poly-substituted with groups independently selected from, but not limited to, deuterium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C15 heteroaryl, substituted or unsubstituted amine, and the like, preferably with groups selected from, but not limited to, deuterium, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, perylenyl, pyrenyl, benzyl, fluorenyl, 9-dimethylfluorenyl, dianilino, dimethylamino, carbazolyl, 9-phenylcarbazolyl, acridinyl, furyl, thienyl, benzofuranyl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, perylene, pyrenyl, benzyl, fluorenyl, 9-dimethylfluorenyl, dimethylamino, carbazolyl, 9-phenylcarbazolyl, acridinyl, furyl, thienyl, benzothienyl, benzoxazolyl, benzimidazol, Mono-or polysubstitution of groups such as dibenzothienyl, phenothiazinyl, phenoxazinyl, indolyl and the like.
The term "integer selected from 0 to M" as used herein means any one of the integers having a value selected from 0 to M, including 0,1, 2 … M-2, M-1, M. Wherein M means a natural number mentioned in the present application. For example, "p is selected from an integer of 0 to 2" means that p is selected from 0,1, 2; "p is an integer of 0 to 4" means that p is selected from 0,1, 2,3, 4; "p is an integer of 0 to 6" means that p is selected from 0,1, 2,3, 4,5, 6.
The bonding to form a cyclic structure according to the present invention means that two groups are connected to each other by a chemical bond. As exemplified below:
Figure BDA0002569338510000061
in the present invention, the rings bonded to form the ring structure may be five-membered rings or six-membered rings or fused rings, such as phenyl, naphthyl, cyclopentenyl, cyclopentyl, cyclohexanophenyl, fluorenyl, quinolyl, isoquinolyl, dibenzothienyl, phenanthryl or pyrenyl, but not limited thereto.
The invention provides an arylamine organic compound, the molecular structural general formula of which is shown as formula I:
Figure BDA0002569338510000062
wherein, L is selected from one of single bond, substituted or unsubstituted C6-C25 arylene, substituted or unsubstituted C2-C20 heteroarylene;
Ar1、Ar2、Ar3、Ar4at least one of them is a group represented by the following formula II, and the others are independently selected from one of substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl:
Figure BDA0002569338510000071
wherein X is selected from O, S, Se, N-Ra、C-RbRcOne of (1), RaOne selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C2-C20 heteroaryl; rb、RcThe same or different one selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl, or Rb、RcBonded together to form a ring structure;
the ring A is selected from one of no, benzene ring and naphthalene ring;
R1one selected from H, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C2-C20 heteroaryl;
when ring A is selected from null, p is selected from an integer from 0 to 2; when ring A is selected from a benzene ring, p is selected from an integer of 0 to 4; when ring A is selected from naphthalene rings, p is selected from an integer of 0 to 6;
Lnone selected from single bond, substituted or unsubstituted C6-C25 arylene, and substituted or unsubstituted C2-C20 heteroarylene.
Preferably, the formula II is selected from one of the groups shown in formulas II-a to II-e below:
Figure BDA0002569338510000072
preferably, Ar is1One selected from the group shown below:
Figure BDA0002569338510000073
wherein R is1One selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl, dibenzofuranyl;
Lnone selected from single bond, phenylene, naphthylene, biphenylene and tolylene;
Raone selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl, dibenzofuranyl.
Preferably, Ar is2、Ar3、Ar4Independently selected from one of the groups shown:
Figure BDA0002569338510000081
wherein R is12One selected from methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, phenyl, tolyl, biphenyl and naphthyl;
Rpselected from deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, acridine, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, pyrenyl, indolyl, benzeneOne of benzothienyl, benzofuranyl, dibenzothienyl and dibenzofuranyl;
q is 0,1 or 2;
L1one selected from the group consisting of formulas (1) to (14):
Figure BDA0002569338510000082
preferably, Ar is2、Ar3、Ar4Independently selected from one of the groups shown:
Figure BDA0002569338510000091
preferably, L is one selected from the group consisting of a single bond, phenylene, naphthylene, biphenylene, terphenylene, tolylene, dimethylphenylene, and anthracenylene.
Preferably, L is selected from a single bond or any one of the following groups:
Figure BDA0002569338510000092
more preferably, the arylamine organic compound of the present invention is selected from any one of the following chemical structures:
Figure BDA0002569338510000101
Figure BDA0002569338510000111
Figure BDA0002569338510000121
Figure BDA0002569338510000131
Figure BDA0002569338510000141
Figure BDA0002569338510000151
Figure BDA0002569338510000161
Figure BDA0002569338510000171
Figure BDA0002569338510000181
the arylamine organic compound disclosed by the formula I is obtained through the following synthetic route:
Figure BDA0002569338510000182
case 1: adding methanesulfonic acid into a flask containing the compound 1-a, stirring for dissolving, stirring for 3 days at room temperature to obtain an intermediate 1-1, dissolving the intermediate 1-1 in dichloromethane, cooling to 0 ℃, adding trifluoromethanesulfonic anhydride to obtain a solid intermediate 1-2, and adding the intermediate 1-2, the intermediate A, the intermediate B, a catalyst, a base, a ligand and a toluene solution in a nitrogen atmosphere to obtain a solution of the formula I/The aromatic amine organic compound.
Case 2: adding methanesulfonic acid into a flask containing compound 1-a, stirring for dissolving, stirring at room temperature for 3 days to obtain intermediate 1-1, dissolving intermediate 1-1 in dichloromethane, cooling to 0 deg.C, and adding trifluoromethanesulfonic anhydrideObtaining a solid intermediate 1-2, adding the intermediate 1-2 and the intermediate A in a nitrogen atmosphere/Intermediate B/Catalyst, alkali, ligand and toluene solution to obtain the arylamine organic compound shown in the chemical formula I.
The arylamine organic compound shown in the formula I can be prepared by combining the steps.
The sources of the raw materials used in the above-mentioned reactions are not particularly limited, and the aromatic amine organic compounds of the present invention can be obtained by using commercially available raw materials or by using preparation methods known to those skilled in the art.
The present invention is not particularly limited to the above-mentioned reaction, and a conventional reaction known to those skilled in the art may be used.
The invention also provides an organic light-emitting device which comprises a cathode, an anode and one or more organic layers arranged between the two electrodes and outside the two electrodes, wherein the organic layer arranged between the cathode and the anode comprises a hole injection layer, a hole transport layer and at least one of an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer; the organic layer disposed outside the cathode and the anode includes a capping layer; the organic layer contains any one or a combination of at least two of the aromatic amine organic compounds.
Preferably, the organic layer of the present invention includes a hole transport layer, and the hole transport layer contains any one or a combination of at least two of the arylamine organic compounds of the present invention.
The light emitting device of the present invention is generally formed on a substrate. The substrate may be any substrate as long as it does not change when forming an electrode or an organic layer, for example, a substrate of glass, plastic, a polymer film, silicon, or the like. When the substrate is opaque, the electrode opposite thereto is preferably transparent or translucent.
In the light-emitting device of the present invention, at least one of the anode and the cathode is transparent or translucent, and preferably, the cathode is transparent or translucent.
The anode material is preferably a material having a large work function so that holes are smoothly injected into the organic material layer, and a conductive metal oxide film, a translucent metal thin film, or the like is often used. Examples of the method for producing the film include a film (NESA or the like) made of a conductive inorganic compound containing indium oxide, zinc oxide, tin oxide, and a composite thereof, such as indium tin oxide (abbreviated as ITO) or indium zinc oxide (abbreviated as IZO), and a method using gold, platinum, silver, copper, or the like. As the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof, or the like can be used. The anode may have a laminate structure of 2 or more layers, and preferably, the anode of the present invention is formed of an opaque ITO-Ag-ITO substrate.
The hole injection layer is to improve the efficiency of hole injection from the anode into the hole transport layer and the light emitting layer. The hole injection material of the present invention may be a metal oxide such as molybdenum oxide, silver oxide, vanadium oxide, tungsten oxide, ruthenium oxide, nickel oxide, copper oxide, or titanium oxide, or a low molecular weight organic compound such as a phthalocyanine-based compound or a polycyano group-containing conjugated organic material, but is not limited thereto. Preferably, the hole injection layer of the present invention is selected from 4,4 '-tris [ 2-naphthylphenylamino ] triphenylamine (abbreviated as 2T-NATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylamine (abbreviated as HAT-CN), 4' -tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), 4 '-tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine (abbreviated as MTDATA), copper (II) phthalocyanine (abbreviated as CuPc), N' -bis [4- [ bis (3-methylphenyl) amino ] phenyl ] -N, N '-diphenyl-biphenyl-4, 4' -diamine (abbreviated as DNTPD), etc., it may be a single structure made of a single substance, or a single-layer structure or a multi-layer structure made of different substances.
The hole transport layer is a layer having a function of transporting holes. The hole transport material of the present invention is preferably a material having a good hole transport property, and may be selected from small molecular materials such as aromatic amine derivatives, carbazole derivatives, stilbene derivatives, triphenyldiamine derivatives, styrene compounds, butadiene compounds, and the like, and polymeric materials such as poly-p-phenylene derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, and the like, and the arylamine organic compound provided by the present invention, but is not limited thereto. Preferably, the hole transport layer of the present invention is selected from the group consisting of N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (abbreviated as NPB), N '-di (naphthalene-1-yl) -N, N' -di (phenyl) -2,2 '-dimethylbenzidine (abbreviated as. alpha. -NPD), N' -diphenyl-N, N '-di (3-methylphenyl) -1,1' -biphenyl-4, 4 '-diamine (abbreviated as TPD), 4' -cyclohexyldi [ N, N-di (4-methylphenyl) aniline ] (abbreviated as TAPC), 2,7, 7-tetra (diphenylamino) -9, the 9-spirobifluorene (short for: Spiro-TAD) and the arylamine organic compound provided by the invention can be of a single structure formed by a single substance or of a single-layer structure or a multi-layer structure formed by different substances.
The electron-blocking layer is a layer which transports holes and blocks electrons, and is preferably selected from N, N ' -bis (naphthalen-1-yl) -N, N ' -bis (phenyl) -2,2' -dimethylbenzidine (abbreviated as. alpha. -NPD), 4' -tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (abbreviated as TPD), 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (abbreviated as TAPC), 2,7, 7-tetrakis (diphenylamino) -9, 9-spirobifluorene (abbreviated as Spiro-TAD), and the like, it may be a single structure made of a single substance, or a single-layer structure or a multi-layer structure made of different substances.
The light-emitting layer is a layer having a light-emitting function. The light emitting layer material comprises a light emitting layer host material AND a light emitting layer guest material, preferably, the host material of the present invention is selected from 4,4 '-bis (9-carbazole) biphenyl (CBP for short), 9, 10-bis (2-naphthyl) anthracene (ADN for short), 4-bis (9-carbazolyl) biphenyl (CPB for short), 9' - (1, 3-phenyl) bis-9H-carbazole (mCP for short), 4 '-tris (carbazol-9-yl) triphenylamine (TCTA for short), 9, 10-bis (1-naphthyl) anthracene (alpha-AND for short), N' -bis- (1-naphthyl) -N, N '-diphenyl- [1,1':4', 1':4', 1' -tetrabiphenyl ] -4,4' -diamino (4P-NPB for short), 1,3, 5-tri (9-carbazolyl) benzene (TCP for short) and the like, which can be a single-layer structure formed by a single substance or a single-layer structure or a multi-layer structure formed by different substances.
The guest material of the light-emitting layer of the present invention may include one material or a mixture of two or more materials, and the light-emitting material is classified into a blue light-emitting material, a green light-emitting material, and a red light-emitting material. Preferably, the luminescent material of the present invention is a blue luminescent material, and the object of the blue luminescent layer is selected from (6- (4- (diphenylamino (phenyl) -N, N-diphenylpyrene-1-amine) (DPAP-DPPA for short), 2,5,8, 11-tetra-tert-butylperylene (TBPe for short), 4' -bis [4- (diphenylamino) styryl ] perylene]Biphenyl (BDAVBi for short), 4' -di [4- (di-p-tolylamino) styryl]Biphenyl (DPAVBi for short), bis (2-hydroxyphenyl pyridine) beryllium (Bepp for short)2) Bis (4, 6-difluorophenylpyridine-C2, N) picolinoyiridium (FIrpic).
The doping ratio of the host material and the guest material of the light-emitting layer is preferably varied depending on the materials used, and the doping film thickness 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 hole blocking layer is a layer that transports electrons and blocks holes, and is preferably selected from 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (abbreviated as BCP), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (abbreviated as TPBi), and tris (8-hydroxyquinoline) aluminum (III) (abbreviated as Alq)3) 8-hydroxyquinoline-lithium (Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), and the like, which may be a single structure composed of a single substance or a single-layer structure or a multi-layer structure composed of different substances.
The electron transport layer is a layer having a function of transporting electrons, and functions to inject electrons and balance carriers. The electron transport material can be selected from known oxadiazole derivatives, anthraquinone dimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinone dimethane and derivatives thereof, fluorenone derivatives, p-benzoquinone derivatives, 8-hydroxyquinoline and gold of derivatives thereofThe electron transport layer is preferably selected from 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (abbreviated as BCP), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (abbreviated as TPBi), and tris (8-hydroxyquinoline) aluminum (III) (abbreviated as Alq)3) 8-hydroxyquinoline-lithium (Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), and the like, which may be a single structure composed of a single substance or a single-layer structure or a multi-layer structure composed of different substances.
The electron injection layer material is a material that assists the injection of electrons from the cathode into the organic layer. The best choice of material is usually a corrosion resistant high work function metal as the cathode, with Al and Ag being common materials. Electron injection materials have been developed to date and include two types; one type is an alkali metal compound, such as lithium oxide (Li)2O), lithium boron oxide (LiBO)2) Cesium carbonate (Cs)2CO3) Potassium silicate (K)2SiO3) And the optimal thickness is generally 0.3-1.0 nm, and the device formed by the compound can reduce the driving voltage and improve the efficiency of the device. In addition, acetate compounds of alkali metals (CH)3COOM, where M is Li, Na, K, Rb, Cs) also have similar effects. Another class is alkali metal fluorides (MF, where M is Li, Na, K, Rb, Cs), and if Al is used as the cathode material, the optimum thickness of these materials is typically less than 1.0 nm. Preferably, the electron injection layer according to the present invention may be selected from LiF.
In the cathode material, a metal material having a small work function is generally preferable in order to inject electrons into the electron injection/transport layer or the light-emitting layer. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like, alloys of 2 or more of these metals, or alloys of 1 or more of these metals and 1 or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite, or graphite intercalation compounds, and the like can be used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy. The cathode may have a laminated structure of 2 or more layers. The cathode can be prepared by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Among them, when light emission of the light-emitting layer is extracted from the cathode, the light transmittance of the cathode is preferably more than 10%. It is also preferable that the sheet resistivity of the cathode is several hundred Ω/□ or less, and the film thickness is usually 10nm to 1 μm, preferably 50 to 200 nm.
The covering layer material is used for reducing the total emission loss and waveguide loss in the OLED device and improving the light extraction efficiency. Alq may be used as the cover layer material of the present invention3TPBi, any one of the compounds CP-1 to CP-9 or a combination of at least two of them. Preferably, the coating material of the present invention may be selected from Alq3。
Figure BDA0002569338510000221
The cathode of the invention adopts Ag or Mg-Ag alloy or thin Al.
Preferably, the hole transport layer material of the present invention is selected from any one or a combination of at least two of any one of the arylamine organic compounds of the present invention.
The film thicknesses of the hole transporting layer and the electron transporting layer may be selected as appropriate depending on the materials used, and may be selected so as to achieve appropriate values of the driving voltage and the light emission efficiency. Therefore, the film thicknesses of the hole transporting layer and the electron transporting layer are, for example, 1nm to 1um, preferably 2nm to 500nm, and more preferably 5nm to 200 nm.
The order and number of layers to be stacked and the thickness of each layer can be appropriately selected in consideration of the light emission efficiency and the lifetime of the device.
The organic light-emitting device of the present invention preferably has a structure in which: substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode/capping layer. However, the structure of the organic light emitting device is not limited thereto. The organic light-emitting device can be selected and combined according to the parameter requirements of the device and the characteristics of materials, and part of organic layers can be added or omitted.
The method for forming each layer in the organic light-emitting device is not particularly limited, and any one of vacuum evaporation, spin coating, vapor deposition, blade coating, laser thermal transfer, electrospray, slit coating, and dip coating may be used, and in the present invention, vacuum evaporation is preferably used.
The organic light-emitting device can be widely applied to the fields of panel display, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, signal lamps and the like.
The invention is explained in more detail by the following examples, without wishing to restrict the invention accordingly. 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 inventive effort.
Preparation and characterization of the Compounds
Description of raw materials, reagents and characterization equipment:
the raw materials used in the following examples are not particularly limited, and may be commercially available products or prepared by methods known to those skilled in the art.
The mass spectrum is obtained by using AXIMA-CFRplus matrix assisted laser desorption ionization flight mass spectrometer of KratosAnalytical company of the Shimadzu group, and chloroform is used as a solvent;
the element analysis uses a VarioELcube type organic element analyzer of Germany Elementar company, and the mass of the sample is 5-10 mg;
nuclear magnetic resonance (1HNMR Spectroscopy) A nuclear magnetic resonance spectrometer model Bruker-510 (Bruker, Germany), 600MHz, CDCl, was used3As solvent, TMS as internal standard.
EXAMPLE 1 Synthesis of Compound 1
Figure BDA0002569338510000231
Step 1: synthesis of intermediate 1-1
500mL of methanesulfonic acid (MeSO)3H) Was added to a flask containing compound 1-a (100.00g, 438mmol), dissolved with stirring, and the mixture was stirred at room temperature for 3 days. The mixture was then poured into 400 g of ice water, stirred to room temperature, and the filter residue was washed with hot water to give the crude product, which was then dissolved in 60% aqueous ethanol by purification by recrystallization to give pure crystalline solid intermediate 1-1 in a yield (40.08g, 89%) of > 99.5% solid purity by HPLC.
Step 2: synthesis of intermediates 1-2
Intermediate 1-1(30.03g, 97.2mmol) was dissolved in 300mL of dichloromethane and cooled to 0 ℃. Trifluoromethanesulfonic anhydride (13.1mL, 77.8mmol) was added slowly and the reaction was allowed to warm slowly to room temperature for overnight reaction. The resulting mixture was quenched with 0.5 MHCl. The layers were separated and the organic layer was washed sequentially with sodium carbonate solution, water and brine. Evaporation of the volatiles gave the intermediate 1-2 as a pale pink solid in 45.63g (82%) with a purity ≧ 99.6% by HPLC.
Step 3: synthesis of intermediate 1-A
To a 1L reaction flask, toluene (600mL), intermediate 1-b (11.19g, 120mmol), intermediate 1-d (29.64g, 120mmol), palladium acetate (0.222g, 1.0mmol), sodium tert-butoxide (12.20g, 0.129mol), and tri-tert-butylphosphine (3.90mL in toluene) were added in that order under nitrogen. And reacted under reflux for 2 hours. After the reaction is stopped, the mixture is cooled to room temperature, filtered by using kieselguhr, the filtrate is concentrated, recrystallized by using methanol, filtered by suction and rinsed by using methanol to obtain a recrystallized solid, and the intermediate 1-A (25.83g, the yield is about 83 percent) is obtained, and the purity of the solid is not less than 99.3 percent by HPLC (high performance liquid chromatography).
Step 4: synthesis of Compound 1
Under nitrogen protection, a 1L reaction flask was charged with toluene solvent (450ml), 1-A (18.15g, 70mmol), intermediate 1-2(18.32g, 32mmol), and Pd in that order2(dba)3(1008mg，1.10mmol)、BINAP(1.67g, 16.7mmol) and sodium tert-butoxide (9.9g, 100.8mmol), dissolved with stirring and reacted under reflux under nitrogen for 24 hours, after completion of the reaction, the reaction solution was washed with dichloromethane and distilled water and extracted by liquid separation. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed, followed by washing with cyclohexane: separating, purifying and refining ethyl acetate 10:1 by column chromatography as eluent to obtain solid compound 1(18.22g, yield 72%), and purity ≧ 99.4% by HPLC.
Mass spectrum m/z: 790.39 (calculated value: 790.36). Theoretical element content (%) C57H46N2O2: c, 86.55; h, 5.86; n, 3.54; o, 4.05 measured element content (%): c, 86.57; h, 5.84; n, 3.53; and O, 4.06.1H NMR(600MHz,CDCl3)(δ,ppm)：8.02(dd,2H),7.60–7.52(m,6H),7.44(td,2H),7.35(td,2H),7.27–7.20(m,6H),7.12–6.98(m,12H),3.04–2.97(m,2H),2.79–2.78(m,2H),1.40–1.32(m,12H)。1HNMR is shown in FIG. 1. The above results confirmed that the obtained product was the objective product.
EXAMPLE 2 Synthesis of Compound 9
Figure BDA0002569338510000241
The same procedure was repeated except for changing 1-b (aniline) in Synthesis example 1 to 9-b in equimolar amount to give compound 9(17.95g, yield: about 79%) having a solid purity of 99.3% or more by HPLC.
Mass spectrum m/z: 890.42 (calculated value: 890.39). Theoretical element content (%) C65H50N2O2: c, 87.61; h, 5.66; n, 3.14; o, 3.59 measured elemental content (%): c, 87.60; h, 5.67; n, 3.16; and O, 3.57.1H NMR(600MHz,CDCl3)(δ,ppm)：8.37(dd,1H),8.31(dd,1H),7.97(dd,2H),7.95–7.90(m,2H),7.80–7.72(m,3H),7.65(dt,1H),7.60(d,1H),7.58–7.49(m,8H),7.46–7.39(m,6H),7.39–7.30(m,5H),7.15(d,2H),7.11(d,1H),7.05(dd,1H),2.34(dd,2H),2.18(dd,2H),1.32(s,6H),1.26(d,6H)。1HNMR is shown in FIG. 2. The above results prove thatThe obtained product is the target product.
EXAMPLE 3 Synthesis of Compound 30
Figure BDA0002569338510000242
The same procedures were repeated except for changing 1-b (aniline) to 30-b in synthesis example 1 and changing 1-d to 30-d in equimolar amounts to give compound 30(20.47g, yield about 80%) having a purity of 99.4% by HPLC.
Mass spectrum m/z: 970.42 (calculated value: 970.38). Theoretical element content (%) C69H50N2O4: c, 85.34; h, 5.19; n, 2.88; o, 6.59 measured elemental content (%): c, 85.36; h, 5.19; n, 2.86; and O, 6.59.1H NMR(600MHz,CDCl3)(δ,ppm)：8.51(dd,1H),8.47(dd,1H),8.35(d,1H),8.09(d,1H),8.06–8.01(m,4H),7.98(d,1H),7.92(d,1H),7.82(d,1H),7.68(dd,2H),7.59(tt,5H),7.55–7.53(m,2H),7.45–7.43(m,2H),7.39(dd,1H),7.36–7.34(m,2H),7.32–7.27(m,3H),7.24(d,1H),7.18(d,2H),7.14(d,3H),2.38(d,1H),2.29(d,1H),2.09(d,1H),2.04(d,1H),1.31(d,6H),1.31(s,3H),1.27(s,3H),1.25(s,3H)。1HNMR is shown in FIG. 3. The above results confirmed that the obtained product was the objective product.
EXAMPLE 4 Synthesis of Compound 41
Figure BDA0002569338510000251
By replacing 1-d in Synthesis example 1 with 41-d in equimolar amount and carrying out the same procedures, Compound 41(17.85g, yield: 83%) was obtained with a solid purity of 99.2% by HPLC.
Mass spectrum m/z: 842.48 (calculated value: 842.46). Theoretical element content (%) C63H58N2: c, 89.74; h, 6.93; n, 3.32 measured elemental content (%): c, 89.75; h, 6.93; and N, 3.31.1HNMR(600MHz,CDCl3)(δ,ppm)：7.79(dd,2H),7.70(d,1H),7.66(d,1H),7.64–7.58(m,3H),7.56–7.48(m,3H),7.45–7.41(m,2H),7.38(dd,1H),7.24(t,5H),7.13(dd,2H),7.10–7.05(m,6H),7.05–6.97(m,4H),2.28(dd,2H),2.02(dd,2H),1.74(d,6H),1.67(d,6H),1.29(s,3H),1.23(d,9H)。1HNMR is shown in FIG. 4. The above results confirmed that the obtained product was the objective product.
EXAMPLE 5 Synthesis of Compound 63
Figure BDA0002569338510000252
The same procedure was repeated except for changing 1-b (aniline) to 63-b and 1-d to 41-d in synthesis example 1 to give compound 63(16.81g, yield about 78%), and purity ≧ 99.4% by HPLC.
Mass spectrum m/z: 844.48 (calculated value: 844.45). Theoretical element content (%) C61H56N4: c, 86.69; h, 6.68; n, 6.63 measured elemental content (%): c, 86.70; h, 6.65; and N, 6.65.1HNMR(600MHz,CDCl3)(δ,ppm)：8.74(t,2H),8.21(td,2H),7.80(dt,2H),7.66–7.58(m,4H),7.55–7.48(m,4H),7.44(tt,2H),7.37–7.28(m,4H),7.22–7.16(m,2H),7.10(dd,2H),7.03(td,4H),2.99(d,2H),2.77(dd,2H),1.71(dd,12H),1.34(d,12H)。1HNMR is shown in FIG. 5. The above results confirmed that the obtained product was the objective product.
EXAMPLE 6 Synthesis of Compound 86
Figure BDA0002569338510000261
The same procedures were repeated except for changing 1-b (aniline) to 86-b in synthesis example 1 and changing 1-d to 86-d in equimolar amounts to give 86(17.89g, yield about 75%) as a compound having a purity of 99.4% by HPLC.
Mass spectrum m/z: 934.49 (calculated value: 934.44). Theoretical element content (%) C65H62N2S2: c, 83.47; h, 6.68; n, 3.00; o, 6.86 measured elemental content (%): c, 83.48; h, 6.67; and N, 3.01；O，6.85。1H NMR(600MHz,CDCl3)(δ,ppm)：8.45–8.43(m,2H),8.03(dd,2H),7.97–7.90(m,3H),7.83(d,1H),7.55(tt,2H),7.43–7.36(m,3H),7.33–7.30(m,4H),7.28–7.25(m,3H),7.23–7.21(m,2H),7.16–7.12(m,4H),7.08–7.05(m,2H),2.35(d,1H),2.26(d,1H),2.07(d,1H),2.02(d,1H),1.30(s,3H),1.28(d,21H),1.25(s,3H),1.22(s,3H)。1The HNMR is shown in FIG. 6. The above results confirmed that the obtained product was the objective product.
EXAMPLE 7 Synthesis of Compound 130
Figure BDA0002569338510000262
The same procedures were repeated except for changing 1-b (aniline) to 130-b and 1-d to 130-d in synthesis example 1 to obtain 130(19.80g, yield: 71%) as a compound with a solid purity ≧ 98.9% by HPLC.
Mass spectrum m/z: 1092.5 (calculated value: 1092.51). Theoretical element content (%) C81H64N4: c, 88.98; h, 5.90; n, 5.12 measured elemental content (%): c, 88.99; h, 5.90; n, 5.11.1HNMR(600MHz,CDCl3)(δ,ppm)：8.51(dd,1H),8.43(t,1H),8.36(dd,1H),8.14(dd,1H),8.10–8.06(m,4H),7.96(dt,4H),7.90(dt,1H),7.79–7.75(m,2H),7.64–7.56(m,6H),7.51(dt,1H),7.48–7.42(m,10H),7.39–7.31(m,7H),7.29(tt,2H),7.22(dt,1H),6.45(d,1H),6.42–6.37(m,3H),6.22–6.19(m,1H),6.09(d,1H),2.29(d,1H),2.16(d,1H),2.03(d,1H),1.75(d,1H),1.15(s,3H),1.13(s,3H),1.06(s,3H),1.05(s,3H)。1HNMR is shown in FIG. 7. The above results confirmed that the obtained product was the objective product.
EXAMPLE 8 Synthesis of Compound 189
Figure BDA0002569338510000271
Step 1: synthesis of intermediate 1-A
The synthesis of intermediate 1-A was carried out in the same manner as in Synthesis example 1.
Step 2: synthesis of intermediate 189-C
To a 1L reaction flask were added toluene (600mL), intermediate 1-A (11.00g, 40mmol), intermediate 1-2(22.88g, 40mmol), palladium acetate (0.074g, 0.33mmol), sodium tert-butoxide (4.09g, 0.043mol), and tri-tert-butylphosphine (1.32mL of 1.0M in toluene) in that order under nitrogen. And reacted under reflux for 2 hours. After the reaction is stopped, the mixture is cooled to room temperature, filtered by using kieselguhr, the filtrate is concentrated, recrystallized by using methanol, filtered by suction and rinsed by using methanol to obtain a recrystallized solid, and the intermediate 189-C (23.15g, the yield is about 85 percent) is obtained, and the purity of the solid is not less than 98.7 percent through HPLC (high performance liquid chromatography).
Step 3: synthesis of Compound 189
A1L reaction flask was charged with toluene solvent (450ml), 189-B (6.08g, 36mmol), intermediate 189-C (21.79g, 32mmol), and Pd in that order under nitrogen2(dba)3(990mg, 1.08mmol), BINAP (1.65g, 16.5mmol) and sodium tert-butoxide (9.9g, 100.8mmol), were dissolved with stirring and reacted under reflux under nitrogen for 24 hours, after completion of the reaction, the reaction solution was washed with dichloromethane and distilled water and extracted by separation. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed, followed by washing with cyclohexane: separating, purifying and refining ethyl acetate 10:1 by column chromatography as eluent to obtain solid compound 189(14.80g, yield 66%), and purity ≧ 99.1% by HPLC.
Mass spectrum m/z: 700.40 (calculated value: 700.35). Theoretical element content (%) C51H44N2O: c, 87.39; h, 6.33; n, 4.00; o, 2.28 measured elemental content (%): c, 87.40; h, 6.32; n, 4.02; o, 2.26.1H NMR(600MHz,CDCl3)(δ,ppm)：8.03(dd,1H),7.61(d,1H),7.57–7.51(m,2H),7.44(td,1H),7.35(td,1H),7.27–7.21(m,7H),7.15–7.11(m,3H),7.10–7.04(m,9H),7.00(tt,3H),2.33(d,1H),2.24(d,1H),2.06(d,1H),2.01(d,1H),1.29(s,3H),1.27–1.21(m,9H)。1HNMR is shown in FIG. 8. The above results confirmed that the obtained product was the objective product.
Comparative examples 1-2 device preparation examples:
the organic light-emitting device is prepared by a vacuum thermal evaporation method. The experimental steps are as follows: repeatedly washing the ITO-Ag-ITO substrate with a glass cleaning agent, then washing the ITO-Ag-ITO substrate in distilled water for 2 times, ultrasonically washing for 15 minutes, after the washing with the distilled water is finished, ultrasonically washing solvents such as isopropanol, acetone and methanol in sequence, drying at 120 ℃, and conveying to an evaporation plating machine.
Evaporating a hole injection layer 2-TNATA/50nm, evaporating a hole transport layer NPB/30nm, evaporating a luminescent layer (host ADN: mixed with DPAP-DPPA 5%)/30 nm), evaporating an electron transport layer TPBi/30nm, evaporating an electron injection layer LiF/0.5nm, evaporating a cathode Mg-Ag (Mg: Ag doping ratio of 9:1)/20 nm) on a prepared ITO-Ag-ITO electrode in a layer-by-layer vacuum evaporation manner, and then evaporating a cover layer material Alq on a cathode layer3And/60 nm. 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 as follows:
Figure BDA0002569338510000281
comparative example 2: a comparative organic light emitting device 2 was obtained by replacing the hole transport layer material NPB of comparative example 1 with the compound HT-1, and the other steps were the same.
[ application examples 1 to 8]
Application example 1: the hole transport layer material of the organic light emitting device was replaced with compound 1 in example 1 of the present invention.
Application example 2: the hole transport layer material of the organic light emitting device was replaced with compound 9 in example 2 of the present invention.
Application example 3: the hole transport layer material of the organic light emitting device was replaced with compound 30 in example 3 of the present invention.
Application example 4: the hole transport layer material of the organic light emitting device was replaced with compound 41 in example 4 of the present invention.
Application example 5: the hole transport layer material of the organic light emitting device was replaced with the compound 63 in example 5 of the present invention.
Application example 6: the hole transport layer material of the organic light emitting device was replaced with the compound 86 in example 6 of the present invention.
Application example 7: the hole transport layer material of the organic light emitting device was replaced with the compound 130 in example 7 of the present invention.
Application example 8: the hole transport layer material of the organic light emitting device was changed to compound 189 in example 8 of the present invention.
The driving voltage, the luminous efficiency and the CIE color coordinates of the organic light emitting device were tested by combining test software, a computer, a K2400 digital source meter manufactured by Keithley corporation, usa, and a PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa, into a combined IVL test system.
The results of the light emission characteristic test of the obtained organic light emitting device are shown in table 1. Table 1 shows the results of the test of the light emitting characteristics of the light emitting devices prepared by the compounds prepared in the examples of the present invention and the comparative materials.
Table 1 test of light emitting characteristics of light emitting device
Figure BDA0002569338510000291
As can be seen from the results in table 1, the aromatic amine organic compound of the present invention, when applied to an organic light emitting device, particularly as a hole transport layer material, exhibits advantages of high light emitting efficiency and low driving voltage, as compared to comparative examples 1 to 2, and is an organic light emitting material with good performance.
It should be understood that the present invention has been particularly described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the principles of the invention and, therefore, within the scope of the invention.

Claims (7)

1. An arylamine organic compound is characterized in that the molecular structural general formula is shown as formula I:
Figure FDA0003097191070000011
wherein L is selected from single bonds;
Ar1is a group represented by the following formula II:
Figure FDA0003097191070000012
wherein X is selected from O, S, N-Ra、C-RbRcOne of (1), RaOne selected from aryl of C6-C14 and heteroaryl of C3-C12; rb、RcThe same or different one selected from C1-C6 alkyl, C6-C14 aryl, C3-C12 heteroaryl, or Rb、RcBonded to form a fluorenyl group;
the ring A is selected from one of benzene ring and naphthalene ring;
R1one selected from H, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C14 aryl and substituted or unsubstituted C3-C12 heteroaryl, wherein the substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C14 aryl and substituted or unsubstituted C3-C12 heteroaryl are mono-or polysubstituted by groups independently selected from deuterium, C1-C6 alkyl and phenyl;
when ring A is selected from a benzene ring, p is selected from an integer of 0 to 4; when ring A is selected from naphthalene rings, p is selected from an integer of 0 to 6;
ar is2、Ar3、Ar4Independently selected from one of the following groups:
Figure FDA0003097191070000013
wherein R is12One selected from phenyl, tolyl, biphenyl and naphthyl;
Rpselected from deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butylOne of butyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl and pyrenyl;
q is 0,1 or 2;
L1one selected from the group consisting of formulas (1) to (14):
Figure FDA0003097191070000021
Lnselected from single bonds.
2. An arylamine organic compound according to claim 1 wherein the formula ii is selected from one of the following formulae ii-a, ii-c, ii-d, and ii-e:
Figure FDA0003097191070000022
3. an arylamine organic compound according to claim 1, wherein Ar is Ar1One selected from the group shown below:
Figure FDA0003097191070000023
wherein R is1One selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, biphenyl, naphthyl, phenanthryl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl and dibenzofuranyl;
Lnselected from single bonds;
Rais selected from one of phenyl, biphenyl, naphthyl, phenanthryl, dibenzothienyl and dibenzofuryl.
4. An arylamine organic compound according to claim 1, wherein Ar is Ar2、Ar3、Ar4Independently selected from one of the following groups:
Figure FDA0003097191070000031
5. an arylamine organic compound is characterized in that the arylamine organic compound is selected from any one of the following chemical structures:
Figure FDA0003097191070000041
Figure FDA0003097191070000051
Figure FDA0003097191070000061
Figure FDA0003097191070000071
Figure FDA0003097191070000081
Figure FDA0003097191070000091
Figure FDA0003097191070000101
Figure FDA0003097191070000111
Figure FDA0003097191070000121
6. an organic light-emitting device comprising a cathode, an anode, and one or more organic layers disposed between and outside the cathode and the anode, wherein the organic layer disposed between the cathode and the anode comprises at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer; the organic layer disposed outside the cathode and the anode includes a capping layer; the organic layer contains any one or a combination of at least two of the arylamine organic compounds described in any one of claims 1 to 5.
7. An organic light-emitting device according to claim 6, wherein the organic layer comprises a hole transport layer containing any one or a combination of at least two of the arylamine organic compounds according to any one of claims 1 to 5.
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