CN115433240A - Iridium metal complex and application thereof in photoelectric device - Google Patents

Iridium metal complex and application thereof in photoelectric device Download PDF

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CN115433240A
CN115433240A CN202211159185.1A CN202211159185A CN115433240A CN 115433240 A CN115433240 A CN 115433240A CN 202211159185 A CN202211159185 A CN 202211159185A CN 115433240 A CN115433240 A CN 115433240A
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CN115433240B (en
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杨曦
裘伟明
肖立清
陈佳
李冬云
艾田
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Guangzhou Zhuoguang Technology Co ltd
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
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Abstract

The invention relates to an iridium metal complex and application thereof in photoelectric devices. The iridium metal complex provided by the invention contains a benzisoquinoline group in the structure, and when the iridium metal complex is used as a guest material in a light-emitting layer of an organic electronic device, the light-emitting efficiency of the device can be improved, and the service life of the device can be prolonged.

Description

Iridium metal complex and application thereof in photoelectric device
Technical Field
The invention relates to the field of organic photoelectric materials, in particular to an iridium metal complex and application thereof in photoelectric devices.
Background
Organic Light Emitting Diodes (OLEDs), which are carrier double injection type light emitting devices, are also called organic electroluminescent devices. At a certain driving voltage, electrons are injected from the cathode and holes are injected from the anode, and then the two meet at the organic light emitting layer and recombine to form excitons (i.e., hole-electron pairs). The excitons release energy, return to the ground state in the form of radiative transitions, and emit fluorescence or phosphorescence. In order to improve the light emitting efficiency of the organic light emitting diode, various fluorescent and phosphorescent based light emitting material systems have been developed. Organic light emitting diodes using fluorescent materials have high reliability, but the internal electroluminescence quantum efficiency thereof under electric field excitation is limited to 25%. In contrast, since the branching ratio of the singlet excited state and the triplet excited state of the exciton is 1:3, the organic light emitting diode using the phosphorescent material can almost achieve 100% internal emission quantum efficiency. The existing luminescent layer materials mostly adopt a host-guest doping mode, a metal complex is formed by doping a heavy metal center, spin-orbit coupling can be improved, intersystem crossing is easy to occur under the excitation of an electric field, and thus triplet excitation is effectively obtained.
The complex based on the metallic iridium (III) is a material widely used for high-efficiency OLEDs, and has high efficiency and stability. Baldo et al reported the use of fac-tris (2-phenylpyridine) iridium (III) [ Ir (ppy) 3 ]As phosphorescent light emitting material, 4,4'-N, N' -dicarbazole-biphenyl (4,4 '-N, N' -dicarbazole-biphenyl) (CBP) is a high quantum efficiency OLED with a matrix material (appl. Sky blue complex bis [2- (4 ',6' -difluorophenyl) pyridine-N, C2]Iridium (III) picolinate (FIrpic) is another well known phosphorescent dopant material that exhibits very high photoluminescence quantum efficiency of approximately 60% in solution and almost 100% in solid films when doped into a high triplet energy host (appl. Phys. Lett.2001,79,2082). Although iridium (III) systems based on 2-phenylpyridine and derivatives thereof have been used in large amounts for the preparation of OLEDs, there is still a need for improved device performance, in particular lifetime.
Disclosure of Invention
The invention aims to provide a novel iridium metal complex which can be used as a guest material in a light-emitting layer of an organic electronic device, so that the light-emitting efficiency of the device is improved, and the service life of the device is prolonged.
In order to achieve the technical solution of the object of the present invention, the present invention provides an iridium metal complex, as shown in formula (I):
Figure BDA0003858754280000021
wherein:
R 1 、R 2 、R 3 、R 4 、R 5 each occurrence is independently selected from: -H, -D, a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, a linear thioalkoxy group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms, a branched or cyclic thioalkoxy group having 3 to 20C atoms, a silyl group, a ketone group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, an amine group, -CF 3 -Cl, -Br, -F, -I, a substituted or unsubstituted alkenyl group having 2-20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 50 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 50 ring atoms, a substituted or unsubstituted aryloxy group having 6 to 50 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5 to 50 ring atoms, or a combination of these groups;
m is selected from 1 or 2;
n1 is selected from 0, 1,2,3,4, 5, 6 or 7; n2 is selected from 0, 1,2,3 or 4.
Correspondingly, the invention also provides a guest material of a light-emitting layer, which comprises at least one iridium metal complex.
Correspondingly, the invention also provides a mixture, which comprises at least one iridium metal complex and at least another organic functional material, wherein the at least another organic functional material is selected from a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a light-emitting guest material (Emitter), a light-emitting Host material (Host) or an organic dye.
Correspondingly, the invention also provides a composition which comprises at least one arylamine compound or a mixture thereof and at least one organic solvent.
Correspondingly, the invention also provides an organic electronic device which comprises at least one functional layer, wherein the functional layer comprises at least one iridium metal complex or a mixture or a composition prepared from the iridium metal complex or the mixture.
Compared with the prior art, the invention has the remarkable advantages that: the iridium metal complex provided by the invention contains a benzisoquinoline group in the structure to improve charge transmission in an organic electronic device, so that the luminous efficiency of the device is improved, and the service life of the device is prolonged.
Detailed Description
The technical solutions of the present application will be described clearly and completely in conjunction with the embodiments of the present application, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all of the 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 protection scope of the present application. Furthermore, it should be understood that the detailed description and specific examples, while indicating exemplary embodiments of the invention, are given by way of illustration and explanation only, and are not intended to limit the scope of the invention. In this application, the use of directional words such as "upper" and "lower" in the absence of a contrary indication generally refers to upper and lower in the actual use or operating state of the device. In addition, in the description of the present application, the terms "including" and "comprising" mean "including but not limited to," the term "plurality" means "two or more," and the term "and/or" includes any and all combinations of one or more of the associated listed items. Various embodiments of the present application may exist in a range of forms; it is to be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the application; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the stated range, such as 1,2,3,4, 5, and 6, as applicable regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the range so indicated.
The term "and/or", "and/or" as used herein is intended to be inclusive of any one of the two or more items listed in association, and also to include any and all combinations of the items listed in association, including any two or more of the items listed in association, any more of the items listed in association, or all combinations of the items listed in association. It should be noted that when at least three items are connected by at least two conjunctive combinations selected from "and/or", "or/and", "and/or", it should be understood that, in the present application, the technical solutions definitely include the technical solutions all connected by "logic and", and also the technical solutions all connected by "logic or". For example, "A and/or B" includes A, B and three parallel schemes A + B. For another example, the embodiments of "a, and/or, B, and/or, C, and/or, D" include any of A, B, C, D (i.e., all connected by "logical or"), any and all combinations of A, B, C, D, i.e., any two or any three of A, B, C, D, and any and all four combinations of A, B, C, D (i.e., all connected by "logical and").
In the present invention, the aromatic groups, aromatic groups and aromatic ring systems have the same meaning and are interchangeable.
In the context of the present invention, heteroaromatic groups, heteroaromatic and heteroaromatic ring systems have the same meaning and are interchangeable.
In the present invention, the "hetero atom" is a non-carbon atom and may be a N atom, an O atom, an S atom or the like.
In the present invention, "substituted" means that one or more hydrogen atoms in a substituent are substituted by a substituent.
In the present invention, "mono-substituted" means substituted with one substituent, "di-substituted" means substituted with two substituents, "tri-substituted" means substituted with three substituents, "tetra-substituted" means substituted with four substituents, and "penta-substituted" means substituted with five substituents.
In the present invention, when the same substituent is present in plural times, it may be independently selected from different groups. If the general formula contains a plurality of R, R can be independently selected from different groups.
In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood that the defined group may be substituted with one or more substituents R selected from, but not limited to: deuterium atom, cyano group, isocyano group, nitro group or halogen, alkyl group containing 1 to 20C atoms, heterocyclic group containing 3 to 20 ring atoms, aromatic group containing 6 to 20 ring atoms, heteroaromatic group containing 5 to 20 ring atoms, -NR' R ", silane group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, haloformyl group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, trifluoromethyl group, and the above groups may be further substituted with art-acceptable substituents; understandably, R 'and R "in-NR' R" are each independently selected from, but not limited to: H. deuterium atom, cyano group, isocyano group, nitro group or halogen, alkyl group containing 1 to 10C atoms, heterocyclic group containing 3 to 20 ring atoms, aromatic group containing 6 to 20 ring atoms, heteroaromatic group containing 5 to 20 ring atoms. Preferably, R is selected from, but not limited to: deuterium atom, cyano group, isocyano group, nitro group or halogen, alkyl group having 1 to 10C atoms, heterocyclic group having 3 to 10 ring atoms, aromatic group having 6 to 20 ring atoms, heteroaromatic group having 5 to 20 ring atoms, silane group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, haloformyl group, formyl group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, trifluoromethyl group, and the above groups may be further substituted with substituents acceptable in the art.
In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
"aryl or aromatic group" means an aromatic hydrocarbon group derived by removing one hydrogen atom from an aromatic ring compound, and may be a monocyclic aromatic group, or a fused ring aromatic group, or a polycyclic aromatic group, at least one of which is an aromatic ring system for polycyclic ring species. For example, "substituted or unsubstituted aryl group having 6 to 40 ring atoms" means an aryl group containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl group having 6 to 14 ring atoms, and the aryl group is optionally further substituted; suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, perylenyl, acenaphthenyl and derivatives thereof. It will be appreciated that a plurality of aryl groups may also be interrupted by short non-aromatic units (e.g. <10% of non-H atoms, such as C, N or O atoms), such as in particular acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, diarylether systems should also be included in the definition of aryl groups.
"heteroaryl or heteroaromatic group" means that on the basis of an aryl at least one carbon atom is replaced by a non-carbon atom which may be a N atom, O atom, S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" refers to heteroaryl having 5 to 40 ring atoms, preferably substituted or unsubstituted heteroaryl having 6 to 30 ring atoms, more preferably substituted or unsubstituted heteroaryl having 6 to 18 ring atoms, particularly preferably substituted or unsubstituted heteroaryl having 6 to 14 ring atoms, and heteroaryl is optionally further substituted, suitable examples including but not limited to: thienyl, furyl, pyrrolyl, oxadiazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothienyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, o-diazonaphthyl, phenanthridinyl, primidinyl, quinazolinone, dibenzothienyl, dibenzofuranyl, carbazolyl, and derivatives thereof.
In the present invention, "alkyl" may mean a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Phrases containing the term, e.g., "C 1 -C 9 Alkyl "means an alkyl group containing from 1 to 9 carbon atoms, which may, for each occurrence, be independently C 1 Alkyl radical, C 2 Alkyl radical, C 3 Alkyl radical, C 4 Alkyl radical, C 5 Alkyl radical, C 6 Alkyl radical, C 7 Alkyl radical, C 8 Alkyl or C 9 An alkyl group. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-dimethylheptyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, etc,2-hexyldecyl group, 2-octyldecyl group, n-undecyl group, n-dodecyl group, 2-ethyldodecyl group, 2-butyldodecyl group, 2-hexyldodecyl group, 2-octyldodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, 2-ethylhexadecyl group, 2-butylhexadecyl group, 2-hexylhexadecyl group, 2-octylhexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, 2-ethyleicosyl group, 2-butyleicosyl group, 2-hexyleicosyl group, 2-octyleicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, n-triacontyl group and the like.
The term "alkoxy" refers to a group of the structure "-O-alkyl", i.e. an alkyl group as defined above is attached to another group via an oxygen atom. Phrases encompassing this term, suitable examples include, but are not limited to: methoxy (-O-CH) 3 or-OMe), ethoxy (-O-CH) 2 CH 3 or-OEt) and t-butoxy (-O-C (CH) 3 ) 3 or-OtBu).
In the present invention, "+" attached to a single bond represents a connection or a fusion site;
in the present invention, when the attachment site is not specified in the group, it means that an optional attachment site in the group is used as the attachment site;
in the present invention, when the same group contains a plurality of substituents of the same symbol, the substituents may be the same or different from each other, for example
Figure BDA0003858754280000061
The 6R's on the phenyl ring may be the same or different from each other.
In the context of the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached at an optional position on the ring, for example
Figure BDA0003858754280000062
Wherein R is attached to any substitutable site of the phenyl ring.
The terms "combination thereof", "any combination thereof", "combination of groups", "combination" and the like as used herein include all suitable combinations of any two or more of the listed groups.
In the present invention, "further", "still further", "specifically" and the like are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of the present invention.
In the present invention, "optionally", "optional" and "optional" refer to the presence or absence, i.e., to any one of two juxtapositions selected from "present" and "absent". If multiple optional parts appear in one technical scheme, if no special description exists, and no contradiction or mutual constraint relation exists, each optional part is independent.
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.
An iridium metal complex represented by the general formula (I):
Figure BDA0003858754280000063
wherein:
R 1 、R 2 、R 3 、R 4 、R 5 each occurrence is independently selected from: -H, -D, a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, a linear thioalkoxy group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms, a branched or cyclic thioalkoxy group having 3 to 20C atoms, a silyl group, a ketone group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, an amine group, -CF 3 -Cl, -Br, -F, -I, substituted or unsubstitutedSubstituted alkenyl having 2-20 carbon atoms, substituted or unsubstituted aromatic group having 6 to 50 ring atoms, substituted or unsubstituted heteroaromatic group having 5 to 50 ring atoms, substituted or unsubstituted aryloxy group having 6 to 50 ring atoms, substituted or unsubstituted heteroaryloxy group having 5 to 50 ring atoms, or combinations of these groups;
m is selected from 1 or 2;
n1 is selected from 0, 1,2,3,4, 5, 6 or 7; n2 is selected from 0, 1,2,3 or 4.
In one embodiment, R 1 、R 2 、R 3 、R 4 、R 5 Each occurrence is independently selected from: -H, -D, straight-chain alkyl having 1 to 10C atoms, branched or cyclic alkyl having 3 to 10C atoms, silyl, cyano, isocyano, hydroxy, nitro, amino, -CF 3 -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 6 to 30 ring atoms, or a combination of these groups.
In one embodiment, R 3 、R 4 、R 5 Each occurrence is independently selected from: -H, -D, a straight chain alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, a substituted or unsubstituted aromatic group having 6 to 10 ring atoms, a substituted or unsubstituted heteroaromatic group having 6 to 10 ring atoms, or a combination of these groups.
In one embodiment, R 5 Selected from H or D.
In one embodiment, R 3 、R 4 Each occurrence is independently selected from: -H, -D, a straight chain alkyl group having 1 to 6C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, a phenyl group, or a combination of these groups. Preferably, R 3 And R 4 Selected from the same group.
More preferably, R 3 、R 4 Each occurrence is independently selected from H, -D, or the following groups:
Figure BDA0003858754280000071
where denotes the attachment site.
In one embodiment, R 1 、R 2 Each occurrence is independently selected from: -H, -D, straight-chain alkyl having 1 to 10C atoms, branched or cyclic alkyl having 3 to 10C atoms, silyl, cyano, isocyano, hydroxy, nitro, amino, -CF 3 -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 10 ring atoms, a substituted or unsubstituted heteroaromatic group having 6 to 10 ring atoms, or a combination of these groups.
Further, R 1 、R 2 Each occurrence is independently selected from the group consisting of H, -D, straight chain alkyl of 1 to 6C atoms, branched or cyclic alkyl of 3 to 10C atoms, silyl, cyano, isocyano, hydroxy, nitro, amino, -CF 3 -Cl, -Br, -F, -I, or the following groups:
Figure BDA0003858754280000081
wherein: each occurrence of X is independently selected from CR 6 Or N;
R 6 each occurrence is independently selected from: -H, -D, straight-chain alkyl having 1 to 10C atoms, branched or cyclic alkyl having 3 to 10C atoms, silyl, cyano, isocyano, hydroxy, nitro, amino, -CF 3 -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 6 to 30 ring atoms, or a combination of these groups;
* Indicates the attachment site.
Specifically, R 1 、R 2 Each occurrence is independently selected from H, -D, or the following groups:
Figure BDA0003858754280000082
more preferably, R 1 Is selected from H.
In a particular embodiment, the iridium metal complex is selected from the following formulas II-1 to II-8:
Figure BDA0003858754280000083
the iridium metal complexes according to the present invention include, but are not limited to, the following structures:
Figure BDA0003858754280000091
Figure BDA0003858754280000101
Figure BDA0003858754280000111
in one embodiment, the iridium metal complex provided by the application can be used as an organic functional material in a functional layer of an organic electronic device, in particular to a functional layer of an OLED device. The organic functional material may be, but is not limited to, a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a light emitting guest material (guest Emitter), a light emitting Host material (Host Emitter), and an organic dye.
In one embodiment, one iridium metal complex described herein is used in the light emitting layer, and preferably, one iridium metal complex is used in the light emitting layer as a guest material of the light emitting layer.
The present application further provides a mixture comprising at least one iridium metal complex as described above and at least one other organic functional material. The other organic functional material is selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting guest material, a light emitting host material and an organic dye. Wherein the luminophores are selected from singlet state luminophores (fluorescent luminophores) or triplet state luminophores (phosphorescent luminophores) grade organic thermal excitation delayed fluorescence materials (TADF materials). Details of various organic functional materials are described in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of this 3 patent document being hereby incorporated by reference. It is understood that the other organic functional material may be a small molecule organic material and a high polymer material.
In an embodiment, the further organic functional material is selected from host materials. Wherein the weight percentage of the iridium metal complex in the mixture is more than 0 and less than or equal to 25wt%, preferably more than 0 and less than or equal to 15wt%, more preferably more than 0 and less than or equal to 5wt%, and further more preferably more than 0 and less than or equal to 2wt%.
The present application also relates to a composition comprising at least one iridium metal complex or mixture as described above, and at least one organic solvent.
The organic solvent is at least one selected from the group consisting of aromatic or heteroaromatic-based solvents, ester-based solvents, aromatic ketone-based solvents, aromatic ether-based solvents, aliphatic ketones, aliphatic ethers, alicyclic compounds, olefinic compounds, borate compounds, and phosphate compounds.
In at least one embodiment, the organic solvent in the composition is selected from aromatic or heteroaromatic-based solvents.
The aromatic or heteroaromatic-based solvent may be selected from, but is not limited to, at least one of p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisoprene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, alpha-dichloropyridine, 4264- (3-ethyl-phenyl) benzoate, and methyl benzoate.
The ester-based solvent may be selected from, but is not limited to, alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Particularly, at least one of octyl octanoate, diethyl sebacate, diallyl phthalate and isononyl isononanoate is preferable.
The aromatic ketone-based solvent may be selected from the group consisting of, but not limited to, 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof. Wherein, as an example, the derivative may be selected from at least one of, but not limited to, 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, and 2-methylpropiophenone.
The aromatic ether-based solvent may be selected from, but is not limited to, at least one of 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4- (1-propenyl) benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethylnative ether, 1,3-dipropoxybenzene, 1,2,4-trimethoxybenzene, 4- (1-propenyl) -1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenyl ether, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, and ethyl-2-naphthyl ether.
The aliphatic ketone-based solvent may be selected from, but is not limited to, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, 2,6,8-trimethyl-4-nonanone, fenchyne, phorone, isophorone, di-n-amyl ketone, and the like; or an aliphatic ether, for example, at least one of amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
It is to be understood that the organic solvent may be used alone or as a mixed solvent of two or more organic solvents.
In one embodiment, the composition herein includes at least one iridium metal complex or mixture as described above, and at least one organic solvent, and may further include another organic solvent.
The other organic solvent may be selected from, but is not limited to, at least one of methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide (DMSO), tetralin, decalin, and indene.
In one embodiment, the organic solvent suitable for the present application is a solvent having Hansen (Hansen) solubility parameters in the following ranges:
δ d (dispersion force) is in the range of 17.0MPa1/2 to 23.2MPa1/2, particularly in the range of 18.5MPa1/2 to 21.0MPa1/2;
δ p (polar force) in the range of 0.2MPa1/2 to 12.5MPa1/2, particularly in the range of 2.0MPa1/2 to 6.0MPa1/2;
δ h (hydrogen bonding force) is in the range of 0.9MPa1/2 to 14.2MPa1/2, and particularly in the range of 2.0MPa1/2 to 6.0MPa1/2.
In one embodiment, the organic solvent is selected in accordance with the compositions herein taking into account boiling point. In at least some embodiments, the organic solvent has a boiling point of 150 ℃ or higher; preferably equal to or more than 180 ℃; preferably more than or equal to 200 ℃; more preferably more than or equal to 250 ℃; most preferably at least 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads.
It is understood that the organic solvent may be evaporated from the solvent system to form a thin film comprising the organic compound.
In one embodiment, the composition is a solution. In still other embodiments, the composition is a suspension. The solution or suspension may additionally include additives for adjusting viscosity, adjusting film-forming properties, improving adhesion, and the like. The additive may be selected from, but is not limited to, at least one of a surface active compound, a lubricant, a wetting agent, a dispersant, a hydrophobic agent, and a binder.
The composition may also be referred to as an ink.
For the printing process, viscosity and surface tension of the ink are important parameters. Suitable inks have surface tension parameters suitable for a particular substrate and a particular printing process.
In one embodiment, the surface tension of an ink according to the present application at operating temperature or at 25 ℃ is in the range of about 19dyne/cm to about 50dyne/cm; more preferably 22dyne/cm to 35dyne/cm; preferably 25dyne/cm to 33dyne/cm.
In one embodiment, the viscosity of the ink according to the present application ranges from 1cps to 100cps at operating temperature or 25 ℃; preferably 1cps to 50cps; more preferably 1.5cps to 20cps; preferably 4.0cps to 20cps.
It will be appreciated that inks having the surface tensions and viscosities described above will facilitate ink jet printing.
It will be appreciated that the viscosity of the ink can be adjusted in different ways, such as by appropriate solvent selection and concentration of the functional material in the ink. Inks comprising organic compounds according to the present application can be conveniently adjusted by one in the appropriate range according to the printing method used. The composition of the present application comprises the organic compound or mixture in an amount of 0.01 to 15wt%, preferably 0.1 to 10wt%, more preferably 0.2 to 5wt%, most preferably 0.25 to 3wt%.
The application also relates to the use of said composition as a coating or printing ink for the preparation of organic electronic devices. In one embodiment, the composition is used to prepare organic electronic devices by a printing or coating preparation method. The printing or coating may be prepared by, but is not limited to, ink jet printing, gravure printing, jet printing, letterpress printing, screen printing, dip coating, spin coating, knife coating, roll printing, twist roll printing, offset printing, flexographic printing, rotary printing, spray coating, brush coating, pad printing, slot die coating, and the like. Gravure printing, jet printing and ink-jet printing are preferred.
The present application also relates to the use of an iridium metal complex, mixture or composition as described above in an organic electronic device. In one embodiment, the present application provides an organic electronic device comprising at least one functional layer. The functional layer comprises at least one iridium metal complex or mixture as described above, or is prepared from the above composition.
Further, the organic electronic device comprises a cathode, an anode and at least one functional layer. The functional layer comprises at least one iridium metal complex or mixture as described above, or is prepared from the above composition.
The functional layer may be, but is not limited to, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), or a hole blocking layer. Preferably, the functional layer is a light emitting layer. The light emitting layer comprises at least one iridium metal complex or mixture as described above, or is prepared from the composition as described above.
In one embodiment, the light-emitting layer includes a light-emitting host material and a light-emitting guest material, and the light-emitting guest material is the iridium metal complex or the mixture. Further, the mass ratio of the light-emitting layer guest material to the host material is more than or equal to 25%; further, the mass ratio of the light-emitting layer guest material to the host material is more than or equal to 15%; further, the mass ratio of the light-emitting layer guest material to the host material is greater than or equal to 5%.
The Organic electronic device may be, but is not limited to, an Organic Light Emitting Diode (OLED), an Organic photovoltaic cell (OPV), an Organic light Emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an Organic laser, an Organic spintronic device, an Organic sensor, an Organic Plasmon Emitting Diode (Organic plasma Emitting Diode), and the like. Particularly preferred are organic electroluminescent devices such as OLEDs, OLEECs, organic light emitting field effect transistors, and the like. Further particularly preferred is an OLED.
The substrate may be transparent or opaque. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, bulovic et al Nature 1996,380, p29, and Gu et al appl. Phys. Lett.1996,68, p2606. The substrate may also be rigid or elastic. In one embodiment, the substrate is plastic, metal, semiconductor wafer, or glass. Preferably, the substrate has a smooth surface, and a substrate free of surface defects is particularly desirable. In a preferred embodiment, the substrate is flexible, and may be selected from a polymer film or plastic, having a glass transition temperature Tg of 150 ℃ or higher, preferably over 200 ℃, more preferably over 250 ℃, and most preferably over 300 ℃. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
The anode is an electrode for injecting holes, and the anode can easily inject holes into the hole injection layer, or the hole transport layer, or the light emitting layer. The anode may comprise a conductive metal, conductive metal oxide, or conductive polymer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. Examples of anode materials include, but are not limited to: al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present application.
The cathode is an electrode for injecting electrons, and the cathode can easily inject electrons into the electron injection layer, or the electron transport layer, or the light emitting layer. The cathode may comprise a conductive metal or conductive metal oxide. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light-emitting layer or the n-type semiconductor material as an Electron Injection Layer (EIL) or an Electron Transport Layer (ETL) or a Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2eV. In principle, all materials which can be used as cathodes for organic electronic devices are possible as cathode materials for organic electronic devices according to the present application. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy, baF2/Al, cu, fe, co, ni, mn, pd, pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
The OLED may also comprise further functional layers, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of these 3 patent documents being hereby incorporated by reference.
The hole injection layer may facilitate injection of holes from the anode into the hole transport layer, thereby reducing the voltage required to inject holes. The hole injection material is a material that can efficiently receive holes injected from the positive electrode, and it is preferable that the Highest Occupied Molecular Orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the hole transport layer material. Common hole injection materials include, but are not limited to: metalloporphyrins, oligothiophenes, arylamine-based organic materials, hexanitrile-hexaazatriphenylene-based organic materials, and the like.
The hole transport layer may serve to smoothly receive holes injected from the anode or the hole injection layer and transfer the holes to the light emitting layer. Common hole transport materials include, but are not limited to: aromatic amine compounds, styrene compounds, butadiene compounds, conductive polymers, block copolymers having both conjugated and non-conjugated portions, and the like, but are not limited thereto.
The electron blocking layer may be disposed between the hole transport layer and the light emitting layer to block electrons from being transported from the light emitting layer to the hole transport layer, thereby confining holes in the light emitting layer to improve light emitting efficiency. Common electron blocking layer materials include, but are not limited to: triarylamine organic compounds, bicarbazole compounds, or materials known in the art.
The host material for the light-emitting layer includes a fused ring aromatic ring derivative, a heterocyclic ring-containing compound, or the like. Specifically, examples of the fused ring aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, triphenylene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, triazine derivatives, and the like, but are not limited thereto.
In an embodiment, the host material for the light emitting layer is selected from co-host materials, preferably, the co-host material is selected from triphenylene-based derivatives and triazine-based derivatives.
The electron transport layer may serve to smoothly transport electrons to the light emitting layer. The electron transport material is selected from materials having high electron mobility, which can efficiently receive electrons injected from the negative electrode or the electron injection layer. Specific examples thereof may include, but are not limited to: at least one of an Al complex of 8-hydroxyquinoline, a complex comprising Alq3, an organic radical compound, a hydroxyflavone-metal complex, lithium 8-hydroxyquinoline (LiQ), ETM, and a benzimidazole-based compound.
The electron injection layer can promote the injection of electrons from the negative electrode and reduce the voltage required by the injection of the electrons. Specific examples thereof include, but are not limited to: fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, tmPyPB, and the like.
The hole blocking layer may block holes from reaching the electron transport layer, thereby confining electrons in the light emitting layer to improve light emitting efficiency. Specific examples thereof include, but are not limited to, oxadiazole or triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, and the like.
The organic electronic device emits light at a wavelength of between 300 and 1000nm, preferably between 350 and 900nm, and more preferably between 640 and 650 nm.
In one embodiment, the organic electronic device described herein is a solution-type organic electronic device, wherein one or more functional layers thereof are prepared by printing; further, the solution-type organic electronic device is a solution-type OLED.
The present application also relates to the use of the organic electronic device according to the present application in various electronic devices, which may be, but are not limited to, display devices, lighting devices, light sources, sensors, etc.
The application also relates to an electronic device comprising said organic electronic device. The electronic device may be, but is not limited to, a display device, a lighting device, a light source, a sensor, and the like.
The present application will be described in detail with reference to specific examples, which are intended to be part of the present application and are not intended to limit the present application. The present application is not limited to the following examples.
The specific implementation mode is as follows:
example 1: synthesis of Compound 1
Figure BDA0003858754280000171
Synthesis of Compound 1-1:
compound A (16.7g, 100mmol), 2-bromopyridine (15.8g, 100mmol), tris (dibenzylideneacetone) dipalladium (1.73g, 3mmol) and sodium tert-butoxide (19.2g, 200mmol) were weighed out accurately, and the weighed materials were charged into a 1000mL three-necked flask, and about 450mL of anhydrous toluene was added, and after introducing nitrogen gas three times, tri-tert-butylphosphine (12mL, calculated as mass ratio 10) was added dropwise to the reaction system, and then the temperature was raised to 100 ℃ to react for 6 hours. Cooling to room temperature after the raw materials completely react, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, then distilling under reduced pressure to remove redundant solvent, and recrystallizing the crude product by toluene/methanol. Compound 1-1 was obtained in about 14.7g, yield: 60.2 percent. Ms 245.30
Synthesis of Compounds 1-2:
accurately weighing the compound 1-1 (14.6g, 60mmol), adding the compound into a 500mL three-neck flask, adding iridium trichloride monohydrate (3.8g 12mmol), adding ethylene glycol ether (200 mL), pumping in nitrogen for three times, heating to 120 ℃, reacting for 12 hours, cooling the reaction liquid to room temperature, carrying out suction filtration, leaching the filter cake with petroleum ether for several times, and obtaining about 13g of a crude product of the compound 1-2. Yield: synthesis of 90% compound 1:
compound 1-2 (13g, 9mmol) was weighed into a 250mL three-necked flask, sodium carbonate (1.9g, 18mmol), 2,4-pentanedione (0.9g, 9mmol) and then 80mL of dichloromethane and 40mL of methanol were added, nitrogen gas was purged three times, and the temperature was raised to 60 ℃ for 12 hours. After the reaction is finished, washing with water, extracting with dichloromethane, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring column chromatography, wherein the eluent is PE: DCM =5:1 (volume ratio) to obtain about 4.6g of the compound 1. Yield: 25.6 percent. Ms 779.92
Example 2: synthesis of Compound 2
Figure BDA0003858754280000181
Synthesis of Compound 2-1:
compound A (16.7g, 100mmol), 2-bromo-4,6-lutidine (18.6 g, 100mmol), tris (dibenzylideneacetone) dipalladium (1.73g, 3mmol) and sodium tert-butoxide (19.2g, 200mmol) were weighed out accurately, and added to a 1000mL three-necked flask, and about 450mL of anhydrous toluene was added, and after introducing nitrogen gas three times, tri-tert-butylphosphine (plastid ratio 10: 12mL) was added dropwise to the reaction system, and then the temperature was raised to 100 ℃ to react for 6 hours. Cooling to room temperature after the raw materials completely react, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, removing redundant solvent by reduced pressure distillation, and recrystallizing a crude product by toluene/methanol. Compound 2-1 is obtained in about 18.8g, yield: 69.0 percent. Ms 273.35
Synthesis of Compound 2-2:
accurately weighing the compound 2-1 (18.8g, 69mmol), adding the compound into a 500mL three-neck flask, adding iridium trichloride monohydrate (4.4g 13.8mmol), adding 200mL ethylene glycol ether, pumping nitrogen for three times, raising the temperature to 120 ℃, reacting for 12 hours, cooling the reaction liquid to room temperature, performing suction filtration, leaching a filter cake with petroleum ether for several times, and obtaining about 21.5g of a crude product of the compound 2-2. Yield: 80.8 percent.
Synthesis of Compound 2:
compound 2-2 (21.5g, 13.9mmol) was weighed accurately into a 500mL three-necked flask, sodium carbonate (2.9g, 27.8mmol), 2,4-pentanedione (1.4g, 13.9mmol) and then dichloromethane (150 mL), methanol (50 mL) were added, nitrogen gas was introduced three times, and the temperature was raised to 60 ℃ to react for 12 hours. After the reaction is finished, washing with water, extracting with dichloromethane, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel sample-mixing column chromatography, wherein an eluent is PE: DCM =5:1 (volume ratio) to obtain about 5.6g of the compound 2. Yield: 24.1 percent. Ms:836.03.
example 3: synthesis of Compound 7
Figure BDA0003858754280000191
Synthesis of Compound 3-1:
compound A (16.7g, 100mmol), 2-bromo-4-phenylpyridine (23.4g, 100mmol), tris (dibenzylideneacetone) dipalladium (1.73g, 3mmol) and sodium tert-butoxide (19.2g, 200mmol) were weighed out and added to a 1000mL three-necked flask, and about 450mL of anhydrous toluene was added, and after purging with nitrogen three times, tri-tert-butylphosphine (plastid ratio 10: 12mL) was added dropwise to the reaction system, followed by heating to 100 ℃ and reacting for 6 hours. Cooling to room temperature after the raw materials completely react, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, then distilling under reduced pressure to remove redundant solvent, and recrystallizing the crude product by toluene/methanol. Compound 3-1 is obtained in about 21.5g, yield: 67.1 percent. Ms 321.40.
Synthesis of Compound 3-2:
accurately weighing the compound 3-1 (21.5g, 67mmol), adding the compound into a 500mL three-neck flask, adding iridium trichloride monohydrate (4.2g, 13.4 mmol), adding ethylene glycol ether (200 mL), pumping through nitrogen gas for three times, heating to 120 ℃, reacting for 12 hours, cooling the reaction liquid to room temperature, performing suction filtration, leaching the filter cake with petroleum ether for several times, and obtaining about 23.2g of a crude product of the compound 3-2. Yield: 79.8 percent.
Synthesis of compound 7:
compound 3-2 (23.2g, 13.4 mmol) was weighed accurately and charged into a 500mL three-necked flask, sodium carbonate (2.8g, 26.8mmol), 2,4-pentanedione (1.3g, 13.4 mmol) and then dichloromethane (200 mL), methanol (80 mL) were added, nitrogen gas was purged three times, and then the temperature was raised to 60 ℃ for 12 hours. After the reaction is finished, washing with water, extracting with dichloromethane, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel sample-mixing column chromatography, wherein an eluent is PE: DCM =5:1 (volume ratio) to obtain about 5.1g of the compound 7. Yield: 20.4 percent. Ms:931.12.
Example 4: synthesis of compound 20:
Figure BDA0003858754280000201
synthesis of Compound 4-1:
2,5-dibromopyridine (23.7g, 100mmol), 3,5-dimethylbenzeneboronic acid (15g, 100mmol), tetratriphenylphosphine palladium (3.5g, 3mmol) and potassium carbonate (27.6g, 200mmol) are weighed accurately, added to a 1000mL three-neck flask in sequence, about 400mL of toluene and 100mL of water are added, nitrogen is pumped in for three times, and then the temperature is raised to 90 ℃ for reaction overnight. Cooling to room temperature after the raw materials completely react, separating liquid, extracting for three times with ethyl acetate, combining organic phases, and carrying out silica gel mixing column chromatography. The eluent was PE: EA =5:1 (volume ratio) to give compound 4-1 about 20.5g, yield: 78.2 percent. Ms 263.15.
Synthesis of Compound 4-2:
compound 4-1 (20.5g, 78mmol), compound A (13g, 78mmol), tris (dibenzylideneacetone) dipalladium (1.34g, 2.3mmol) and sodium tert-butoxide (14.9g, 156mmol) were weighed out and added to a 1000mL three-necked flask in this order, and about 450mL of anhydrous toluene was added, and after introducing nitrogen gas three times, tri-tert-butylphosphine (the mass ratio was 10: 9.4mL) was added dropwise to the reaction system, and then the temperature was raised to 100 ℃ for reaction for 6 hours. Cooling to room temperature after the raw materials completely react, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, then distilling under reduced pressure to remove redundant solvent, and recrystallizing the crude product by toluene/methanol. About 23.6g of compound 4-2 was obtained, yield: 86.8 percent. Ms:349.45.
Synthesis of Compounds 4-3:
accurately weighing the compound 4-2 (23.5g, 67mmol), adding the compound into a 500mL three-neck flask, adding iridium trichloride monohydrate (4.2g 13.4 mmol), adding ethylene glycol ether (200 mL), pumping through nitrogen gas for three times, heating to 120 ℃, reacting for 12 hours, cooling the reaction liquid to room temperature, performing suction filtration, leaching the filter cake with petroleum ether for several times, and obtaining about 20.5g of a crude product of the compound 4-3. Yield: 66.3 percent.
Synthesis of compound 20:
compound 4-3 (20.5g, 11.1mmol) was weighed accurately and charged into a 500mL three-necked flask, sodium carbonate (2.4g, 22.2mmol), 2,4-pentanedione (1.1g, 11.1mmol) and then dichloromethane (200 mL), methanol (80 mL) were added, and after purging with nitrogen gas three times, the mixture was heated to 60 ℃ for 12 hours. After the reaction is finished, washing with water, extracting with dichloromethane, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel sample-mixing column chromatography, wherein an eluent is PE: DCM =5:1 (volume ratio) to obtain about 4.3g of the compound 8. Yield: 19.6 percent. Ms:988.23.
Example 5: synthesis of Compound 35
Figure BDA0003858754280000211
Synthesis of Compound 5-1:
compound A (16.7g, 100mmol), 2-bromo-5-methylpyridine (18.6g, 100mmol), tris (dibenzylideneacetone) dipalladium (1.73g, 3mmol) and sodium tert-butoxide (19.2g, 200mmol) were weighed out and added to a 1000mL three-necked flask, and about 450mL of anhydrous toluene was added, and after purging with nitrogen three times, tri-tert-butylphosphine (plasmid ratio: 10: 12mL) was added dropwise to the reaction system, and then the reaction was heated to 100 ℃ for 6 hours. Cooling to room temperature after the raw materials completely react, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, removing redundant solvent by reduced pressure distillation, and recrystallizing a crude product by toluene/methanol. Compound 5-1 is obtained in about 20.8g, yield: 80.5 percent. Ms:259.32.
Synthesis of Compound 5-2:
accurately weighing the compound 5-1 (20.8g, 80mmol), adding the compound into a 500mL three-neck flask, adding iridium trichloride monohydrate (5.1g, 116mmol), adding ethylene glycol ether (200 mL), pumping in nitrogen for three times, heating to 120 ℃, reacting for 12 hours, cooling the reaction liquid to room temperature, carrying out suction filtration, leaching a filter cake with petroleum ether for several times, and obtaining about 22.3g of a crude product of the compound 5-2. Yield: and 75 percent.
Synthesis of Compounds 5-3:
compound 5-2 (22.3g, 15mmol) was weighed accurately and charged into a 500mL three-necked flask, sodium carbonate (3.2g, 30mmol), 2,4-pentanedione (1.5g, 15mmol) and then 150mL of dichloromethane and 50mL of methanol were added, nitrogen gas was purged three times, and the temperature was raised to 60 ℃ to react for 12 hours. After the reaction is finished, washing with water, extracting with dichloromethane, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel sample-mixing column chromatography, wherein the eluent is PE: DCM =5:1 (volume ratio) to obtain about 5-3 g of the compound 6.6g. Yield: 27 percent. Ms:807.97.
synthesis of compound 35:
accurately weighing compound 5-3 (6.6 g, 8mmol) sodium carbonate (1.7 g, 16mmol), sequentially adding into a 250mL three-neck flask, adding 50mL ethylene glycol ethyl ether and 10mL heavy water, pumping nitrogen gas for three times, and heating to 100 ℃ for reaction for 12 hours. After the reaction is finished, the excessive solvent is removed by distillation under reduced pressure, silica gel is used for carrying out column chromatography, and the eluent is PE: EA =5:1 (volume ratio) to about 5.4g of the compound 35. Yield: 81.8 percent. Ms 808.97.
Example 6: synthesis of Compound 42
Figure BDA0003858754280000221
Synthesis of compound 42:
compound 20 (4 g,4 mmol) and sodium carbonate (0.85g, 8 mmol) are weighed accurately and added into a 100mL three-neck flask in turn, 30mL of ethylene glycol ether and 5mL of heavy water are added, nitrogen is pumped in for three times, and then the temperature is raised to 100 ℃ for reaction for 12 hours. After the reaction is finished, the excessive solvent is distilled off under reduced pressure, silica gel is stirred for column chromatography, and the eluent is PE: EA =5:1 (volume ratio) to about 3.3g of the compound 42. Yield: 82.5 percent. Ms:989.23.
Example 7: synthesis of Compound 53
Figure BDA0003858754280000231
Synthesis of Compound 7-1:
2,4-dibromopyridine (23.7 g, 100mmol), phenylboronic acid (12.2g, 100mmol), tetratriphenylphosphine palladium (3.5g, 3mmol) and potassium carbonate (27.6g, 200mmol) were weighed accurately, added to a 1000mL three-necked flask, added with about 400mL toluene and 100mL water, pumped with nitrogen three times, and then heated to 90 ℃ for reaction overnight. Cooling to room temperature after the raw materials completely react, separating liquid, extracting for three times with ethyl acetate, combining organic phases, and carrying out silica gel mixing column chromatography. EA =5:1 to give about 18.5g of compound 7-1, yield: 78.7 percent. Ms:235.10.
Synthesis of Compound 7-2:
compound 7-1 (18.3g, 78mmol), compound A (13g, 78mmol), tris (dibenzylideneacetone) dipalladium (1.34g, 2.3mmol) and sodium tert-butoxide (14.9g, 156mmol) were weighed out and added to a 1000mL three-necked flask in this order, and about 450mL of anhydrous toluene was added, and after purging with nitrogen, tri-tert-butylphosphine (plastid ratio: 10: 9.4mL) was added dropwise to the reaction system, and then the temperature was raised to 100 ℃ for 6 hours. Cooling to room temperature after the raw materials completely react, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, removing redundant solvent by reduced pressure distillation, and recrystallizing a crude product by toluene/methanol. Compound 7-2 was obtained in about 21.5g, yield: 86 percent. Ms:321.40.
Synthesis of Compounds 7-3:
accurately weighing the compound 7-2 (21.5g, 67mmol), adding the compound into a 500mL three-neck flask, adding iridium trichloride monohydrate (4.2g 13.4 mmol), adding ethylene glycol ether (200 mL), pumping through nitrogen gas for three times, heating to 120 ℃, reacting for 12 hours, cooling the reaction liquid to room temperature, performing suction filtration, leaching the filter cake with petroleum ether for several times, and obtaining about 20.5g of a crude product of the compound 7-3. Yield: 70.5 percent.
Synthesis of compound 53:
compound 7-3 (20.5g, 11.8mmol) was weighed accurately, charged into a 500mL three-necked flask, sodium carbonate (2.5g, 23.6 mmol) and compound B (2.5g, 11.8mmol) were added, and then 200mL of methylene chloride and 80mL of methanol were added, and after introducing nitrogen gas three times, the mixture was heated to 60 ℃ to react for 12 hours. After the reaction is finished, washing with water, extracting with dichloromethane, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel sample-mixing column chromatography, wherein an eluent is PE: DCM =5:1 (volume ratio) to obtain about 4.6g of the compound 53. Yield: 37.5 percent. Ms:1040.31.
Example 8: synthesis of Compound 62
Figure BDA0003858754280000241
Synthesis of Compound 8-1:
2,4-dibromopyridine (23.7 g, 100mmol), 3,5-dimethylphenylboronic acid (15g, 100mmol), tetratriphenylphosphine palladium (3.5g, 3mmol) and potassium carbonate (27.6g, 200mmol) were accurately weighed, added to a 1000mL three-necked flask in sequence, about 400mL of toluene and 100mL of water were added, nitrogen gas was pumped in three times, and then the temperature was raised to 90 ℃ for reaction overnight. Cooling to room temperature after the raw materials completely react, separating liquid, extracting for three times with ethyl acetate, combining organic phases, and carrying out silica gel mixing column chromatography. Eluent PE: EA =5:1 (volume ratio) gave compound 8-1 about 20.5g, yield: 78.2 percent. Ms:263.15.
Synthesis of Compound 8-2:
compound 8-1 (20.5g, 78mmol), compound A (13g, 78mmol), tris (dibenzylideneacetone) dipalladium (1.34g, 2.3mmol) and sodium tert-butoxide (14.9g, 156mmol) were weighed out accurately, added to a 1000mL three-necked flask, and about 450mL of anhydrous toluene was added, and after purging with nitrogen three, tri-tert-butylphosphine (10 to 9.4mL in terms of plastid ratio) was added dropwise to the reaction system, and then the temperature was raised to 100 ℃ to react for 6 hours. Cooling to room temperature after the raw materials completely react, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, then distilling under reduced pressure to remove redundant solvent, and recrystallizing the crude product by toluene/methanol. About 23.6g of compound 8-2 was obtained, yield: 86.8 percent. Ms:349.45.
Synthesis of Compounds 8-3:
accurately weighing the compound 8-2 (23.5g, 67mmol), adding the compound into a 500mL three-neck flask, adding iridium trichloride monohydrate (4.2g 13.4 mmol), adding ethylene glycol ether (200 mL), pumping in nitrogen gas for three times, heating to 120 ℃, reacting for 12 hours, cooling the reaction liquid to room temperature, performing suction filtration, leaching the filter cake with petroleum ether for several times, and obtaining about 20.5g of the crude product of the compound 8-3. Yield: 66.3 percent.
Synthesis of compound 62:
compound 8-3 (20.5g, 11.1mmol) was weighed accurately and charged into a 500mL three-necked flask, sodium carbonate (2.4g, 22.2mmol) and compound C (2.6g, 11.1mmol) were added, followed by addition of 200mL of methylene chloride and 80mL of methanol, and after purging with nitrogen gas three times, the mixture was heated to 60 ℃ and reacted for 12 hours. After the reaction is finished, washing with water, extracting with dichloromethane, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel sample-mixing column chromatography, wherein an eluent is PE: DCM =5:1 (volume ratio) to obtain about 5.1g of the compound 62. Yield: 40.9 percent. Ms:1124.46.
Preparing a device:
the structure of the device is as follows: ITO/HIL (30 nm)/HTL (60 nm)/EBL (10 nm)/EML (40 nm)/ETL (30 nm)/EIL (1 nm)/cathode (100 nm).
The EML consists of H-Host, E-Host and a guest material metal complex, the mass ratio of the H-Host to the E-Host is 6:4, and the doping amount of the metal complex is 10% (w/w) of the total mass of the H-Host and the E-Host. Light-emitting layer guest material iridium metal complex (1) or (2) or (7) or (20) or (35) or (42) or (53) or (62) or REF prepared according to the embodiment of the present invention is used. The ETL consisted of a 40% (w/w) ETM doped with LiQ (8-hydroxyquinoline-lithium).
The OLED device uses the following material structure:
Figure BDA0003858754280000251
REF synthesis reference CN110229192a.
Preparation of OLED device
1) And cleaning the ITO conductive glass anode layer, then ultrasonically cleaning the ITO conductive glass anode layer for 15 minutes by using deionized water, acetone and isopropanol, and then treating the ITO conductive glass anode layer in a plasma cleaner for 5 minutes to improve the work function of the electrode.
2) And evaporating a hole injection layer material HIM on the ITO anode layer by a vacuum evaporation mode, wherein the thickness of the hole injection layer material HIM is 30nm.
3) On the hole injection layer, a hole transport material HTM was deposited by vacuum evaporation to a thickness of 60nm.
4) And evaporating an electron blocking material EBM on the hole transport layer in a vacuum evaporation mode, wherein the thickness of the EBM is 10nm.
5) And evaporating a luminescent layer material on the electron barrier layer by a vacuum evaporation mode, wherein the thickness of the luminescent layer material is 40nm.
6) The electron transport material was deposited on the light-emitting layer by vacuum evaporation to a thickness of 30nm.
7) On the electron transport layer, an electron injection layer Liq was vacuum-evaporated to a thickness of 1nm.
8) And a cathode Al layer is vacuum-evaporated on the electron injection layer, and the thickness of the cathode Al layer is 100nm.
9) Encapsulation the devices were encapsulated with uv curable resin in a nitrogen glove box.
Wherein: the evaporation rate of the hole injection layer, the hole transport layer, the luminescent layer, the electron transport layer and the electron injection layer is
Figure BDA0003858754280000262
A cathode layer having a vapor deposition rate of
Figure BDA0003858754280000263
And(s) in the presence of a catalyst. High vacuum of 1X 10 -6 Millibar.
Characterization of OLED devices
The current-voltage-luminance (JVL) characteristics of OLED devices 1 to 8 and OLED-REF were characterized by characterizing the device while recording important parameters such as external quantum efficiency and device lifetime. LT95@1000nits is the time for luminance to drop from the initial luminance of 1000nits to 95% of the initial luminance at a constant current. The relative parameters of the OLED device are shown in the following table:
relative data of devices made with different dopants
Figure BDA0003858754280000261
From the data in the above table, it can be known that, compared with a device made of a REF metal complex, when the iridium metal complex material of the present invention is used as a doping material of an EML (light emitting layer), the external quantum efficiency and the device lifetime of an OLED device are both significantly improved. The reason for the beneficial effect is inferred to be that the iridium metal complex provided by the invention contains a benzisoquinoline group for substitution in the structure, so that the charge transmission in the device is facilitated, the charge can be effectively used, the light-emitting efficiency of the device is improved, the starting voltage is reduced, and the service life of the device is prolonged.
If the present invention is further optimized, such as optimizing the device structure, the combination of the HTM, ETM and host material is optimized, the performance, especially the efficiency, the driving voltage and the lifetime of the device will be further improved.
The technical features of the embodiments and examples described above can be combined in any suitable manner, and for the sake of brevity, all possible combinations of the technical features of the embodiments and examples described above are not described, but should be considered within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. An iridium metal complex represented by the general formula (I):
Figure FDA0003858754270000011
wherein:
R 1 、R 2 、R 3 、R 4 、R 5 each occurrence is independently selected from: -H, -D, straight chain alkyl having 1 to 20C atoms, straight chain alkoxy having 1 to 20C atoms, straight chain thioalkoxy having 1 to 20C atoms a branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms, a branched or cyclic thioalkoxy group having 3 to 20C atoms silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, amine, -CF 3 -Cl, -Br, -F, -I, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aromatic radical having 6 to 50 ring atoms, substituted or unsubstituted heteroaromatic radical having 5 to 50 ring atoms, substituted or unsubstituted aryloxy having 6 to 50 ring atoms, substituted or unsubstituted heteroaryloxy having 5 to 50 ring atoms, or a group of these radicalsCombining;
m is selected from 1 or 2;
n1 is selected from 0, 1,2,3,4, 5, 6 or 7;
n2 is selected from 0, 1,2,3 or 4.
2. An iridium metal complex according to claim 1 wherein R is 1 、R 2 、R 3 、R 4 、R 5 Each occurrence is independently selected from: -H, -D, straight-chain alkyl having 1 to 10C atoms, branched or cyclic alkyl having 3 to 10C atoms, silyl, cyano, isocyano, hydroxy, nitro, amino, -CF 3 -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 6 to 30 ring atoms, or a combination of these groups.
3. An iridium metal complex according to claim 2 wherein R is 3 、R 4 Independently for each occurrence-H, -D, a straight chain alkyl group having 1 to 6C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, a phenyl group, or a combination of these groups.
4. An iridium metal complex according to claim 2 wherein R is 1 、R 2 Each independently selected from H, -D, straight chain alkyl having 1 to 6C atoms, branched or cyclic alkyl having 3 to 10C atoms, silyl, cyano, isocyano, hydroxy, nitro, amino, -CF 3 -Cl, -Br, -F, -I, or the following groups:
Figure FDA0003858754270000021
wherein: x is independently selected from CR for each occurrence 6 Or N;
R 6 each occurrence is independently selected from: -H, -D, straight chain alkyl with 1 to 10C atoms, with 3Branched or cyclic alkyl, silyl, cyano, isocyano, hydroxy, nitro, amino, -CF up to 10C atoms 3 -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 6 to 30 ring atoms, or a combination of these groups;
* Indicates the attachment site.
5. An iridium metal complex according to claim 2 selected from the following structures: r 1 、R 2 Each occurrence is independently selected from H, -D, or the following group:
Figure FDA0003858754270000022
wherein: * Indicates the attachment site.
6. An iridium metal complex according to claim 1, selected from the following compounds:
Figure FDA0003858754270000023
Figure FDA0003858754270000031
Figure FDA0003858754270000041
Figure FDA0003858754270000051
7. a mixture comprising at least one iridium metal complex according to any one of claims 1 to 6 and at least one further organic functional material selected from a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting guest material, a light emitting host material or an organic dye.
8. A composition comprising an iridium metal complex according to any one of claims 1 to 6 or a mixture according to claim 7, and at least one organic solvent.
9. An organic electronic device comprising at least one functional layer, wherein said functional layer comprises an iridium metal complex as defined in any one of claims 1 to 6 or a mixture as defined in claim 7, or is prepared from the composition of claim 8.
10. An organic electronic device according to claim 9, wherein: the organic electronic device is selected from an organic light-emitting diode, an organic photovoltaic cell, an organic light-emitting cell, an organic field effect tube, an organic laser, an organic spinning electronic device, an organic sensor and an organic plasmon emission diode.
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