CN111039987A - Organic transition metal complex, polymer, mixture, composition and organic electronic device - Google Patents

Organic transition metal complex, polymer, mixture, composition and organic electronic device Download PDF

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CN111039987A
CN111039987A CN201911243934.7A CN201911243934A CN111039987A CN 111039987 A CN111039987 A CN 111039987A CN 201911243934 A CN201911243934 A CN 201911243934A CN 111039987 A CN111039987 A CN 111039987A
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carbon atoms
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transition metal
metal complex
dried
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梁志明
颜彩鹃
黄宏
潘君友
陈思航
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Guangzhou Chinaray Optoelectronic Materials Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd

Abstract

The invention discloses an organic transition metal complex, a polymer, a mixture, a composition and an organic electronic device. The organic transition metal complex has a structural general formula shown in a chemical formula (1), is a metal organic complex luminescent material which is simple to synthesize, novel in structure and good in performance, has good luminescent performance, long service life and high stability, is convenient for realizing an OLED device with high efficiency, high brightness and high stability, and provides good material options for full-color display and illumination application.

Description

Organic transition metal complex, polymer, mixture, composition and organic electronic device
The present application claims priority from the chinese patent application entitled "organic transition metal complexes, polymers, mixtures, compositions and organic electronic devices thereof" filed by the chinese patent office on 2018, 12, month 17, application No. 201811543657.7, which is incorporated herein by reference in its entirety.
Technical Field
The invention relates to the field of organic electroluminescence, in particular to an organic transition metal complex, a polymer, a mixture, a composition and an organic electronic device.
Background
Organic Light Emitting Diodes (OLEDs), in flat panel display and lighting applications, have the advantages of low cost, light weight, low operating voltage, high brightness, color tunability, wide viewing angle, easy assembly onto flexible substrates, and low power consumption, and thus have become the most promising display technology. 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% of internal emission quantum efficiency. For small molecule OLEDs, triplet excitation is efficiently obtained by doping with heavy metal centers, which improves spin-orbit coupling and facilitates intersystem crossing to the triplet state.
The complex based on the metallic iridium (III) is a material widely used for high-efficiency OLEDs, and has higher efficiency and stability. Baldo et al reported the use of fac-tris (2-phenylpyridine) iridium (III) [ Ir (ppy)3]4,4 '-N, N' -dicarbazole-biphenyl (4,4 '-N, N' -dicarbazole-biphen as phosphorescent light-emitting materialyl) (CBP) high quantum efficiency OLEDs which are matrix materials (appl. phys. lett.1999,75, 4). Another example of a phosphorescent light-emitting material is the sky-blue complex bis [2- (4 ', 6' -difluorophenyl) pyridine-N, C2]Iridium (III) picolinate (FIrpic), which, when doped into a high triplet energy host, exhibits very high photoluminescence quantum efficiencies of about 60% in solution and almost 100% in solid films (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.
It is therefore desirable to develop new high performance metal complexes to further improve device performance.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the stability of the metal organic complex and the lifetime of the organic light emitting device need to be improved, and the present invention aims to provide an organic transition metal complex, which is a kind of metal organic complex light emitting material with simple synthesis, novel structure and good performance, and has good light emitting performance, long lifetime and high stability.
The technical scheme provided by the invention is as follows,
an organic transition metal complex having a general structural formula shown in chemical formula (1):
Figure BDA0002307000190000011
wherein:
m is a metal atom which is iridium, gold, platinum, ruthenium, rhodium, osmium, rhenium, nickel, copper, silver, zinc, tungsten or palladium;
each L is independently an ancillary ligand;
n is selected from 1,2 or 3; m is selected from 0 or 1 or 2;
each Ar1Independently from each other: r1Substituted or unsubstituted aromatic radical having 5 to 20 ring atoms, R1Substituted or unsubstituted heteroaromatic radical having 5 to 20 ring atoms or R1Substituted or unsubstituted non-aromatic with 5 to 20 ring atomsA ring system;
Ar2、Ar3、Ar4independently selected from R1Substituted or unsubstituted aromatic radical having 5 to 6 ring atoms, R1Substituted or unsubstituted heteroaromatic radical having 5 to 6 ring atoms or R1A substituted or unsubstituted non-aromatic ring system having 5 to 6 ring atoms;
x is selected from CR1Or N;
R1selected from the group consisting of hydrogen, deuterium, halogen, linear alkanes having 1 to 30 carbon atoms, branched alkanes having 1 to 30 carbon atoms, linear alkenes having 1 to 30 carbon atoms, branched alkenes having 1 to 30 carbon atoms, alkane ethers having 1 to 30 carbon atoms, aromatic groups having 1 to 30 carbon atoms, heteroaromatic groups having 1 to 30 carbon atoms or non-aromatic ring systems having 1 to 30 carbon atoms.
The invention also relates to a polymer comprising at least one repeating unit, said repeating unit comprising the structure of the organic transition metal complex as defined above.
The invention also relates to mixtures comprising an organic transition metal complex or polymer as defined above and at least one organic functional material selected from the group consisting of Hole Injection Materials (HIM), Hole Transport Materials (HTM), Electron Transport Materials (ETM), Electron Injection Materials (EIM), Electron Blocking Materials (EBM), Hole Blocking Materials (HBM), luminescent materials (Emitter), Host materials (Host) and dopant materials (Dopants).
The invention also relates to a composition comprising an organic transition metal complex as defined above or a polymer as defined above and at least one organic solvent.
The invention also relates to an organic electronic component comprising an organic transition metal complex as described above or a polymer as described above.
Compared with the prior art, the invention has the following beneficial effects:
the organic transition metal complex is used in OLED, especially as the doping material of the luminous layer, and can provide higher luminous efficiency and device life. The ligand of the quinary ring with a specific structure can prolong the whole length of the complex and increase the light-emitting plane in a specific direction, so that the light-emitting efficiency is improved, and the stability is good. And different atoms can be matched, so that different light colors can be adjusted, and more saturated light colors can be obtained.
Detailed Description
The invention provides an organic transition metal complex, a corresponding mixture and a composition, and application in an organic electronic device, and the invention is further detailed below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the present invention, the composition and the printing ink, or ink, have the same meaning and are interchangeable.
In the present invention, the Host material, Matrix material, Host or Matrix material have the same meaning and are interchangeable with each other.
In the present invention, the metal-organic complex, and the organic transition metal complex have the same meanings and may be interchanged.
The invention relates to an organic transition metal complex, which has a general structural formula shown as a chemical formula (1):
Figure BDA0002307000190000021
wherein:
m is a metal atom which is iridium, gold, platinum, ruthenium, rhodium, osmium, rhenium, nickel, copper, silver, zinc, tungsten or palladium;
each L is independently an ancillary ligand;
n is selected from 1,2 or 3; m is selected from 0 or 1 or 2;
each Ar1Independently from each other: r1Substituted or unsubstituted aromatic radical having 5 to 20 ring atoms, R1Substituted or unsubstituted with 5 to 20 ring atomsOr R1A substituted or unsubstituted non-aromatic ring system having 5 to 20 ring atoms;
Ar2、Ar3、Ar4independently selected from R1Substituted or unsubstituted aromatic radical having 5 to 6 ring atoms, R1Substituted or unsubstituted heteroaromatic radical having 5 to 6 ring atoms or R1A substituted or unsubstituted non-aromatic ring system having 5 to 6 ring atoms;
x is selected from CR1Or N;
R1selected from the group consisting of hydrogen, deuterium, halogen, linear alkanes having 1 to 30 carbon atoms, branched alkanes having 1 to 30 carbon atoms, linear alkenes having 1 to 30 carbon atoms, branched alkenes having 1 to 30 carbon atoms, alkane ethers having 1 to 30 carbon atoms, aromatic groups having 1 to 30 carbon atoms, heteroaromatic groups having 1 to 30 carbon atoms or non-aromatic ring systems having 1 to 30 carbon atoms.
The aromatic group means a hydrocarbon group containing at least one aromatic ring, and includes monocyclic groups and polycyclic ring systems. Heteroaromatic groups refer to hydrocarbon groups (containing heteroatoms) that contain at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. At least one of these rings of the polycyclic ring is an aromatic group or a heteroaromatic group. For the purposes of the present invention, aromatic or heteroaromatic groups include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aryl or heteroaryl groups are interrupted by short nonaromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9,9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are likewise considered aromatic ring systems for the purposes of the present invention.
Specifically, examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, and derivatives of the above ring systems.
Specifically, examples of heteroaromatic groups are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primary pyridine, quinazoline, quinazolinone, and derivatives thereof.
For the purposes of the present invention, non-aromatic ring systems contain 1 to 10, preferably 1 to 6, carbon atoms in the ring system and include not only saturated but also partially unsaturated ring systems which may be unsubstituted or mono-or polysubstituted by any of the radicals R which may be identical or different on each occurrence and may also contain one or more heteroatoms, preferably Si, N, P, O, S and/or Ge, particularly preferably selected from Si, N, P, O and/or S. These may be, for example, cyclohexyl-like or piperidine-like systems, but also cyclooctadiene-like cyclic systems. The term also applies to fused non-aromatic ring systems.
R is selected from (1) C1-C10 alkyl, and particularly preferably refers to the following groups: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoromethyl, 2,2, 2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl; (2) C1-C10 alkoxy, particularly preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2-methylbutoxy; (3) C2-C10 aryl or heteroaryl, which may be monovalent or divalent depending on the application, particularly preferred are the following groups: benzene, naphthalene, anthracene, pyrene, chrysene, perylene, fluoranthene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzofluorene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalimidazole, oxazole, benzoxazole, naphthoxazole, anthraoxazole, phenanthroizole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, benzopyrazine, pyrimidine, benzopyrimidine, quinoxaline, Pyrazine, diazenanthrane, 1, 5-naphthyridine, azocarbazole, benzocarbazine, phenanthroline, 1,2, 3-triazole, 1,2, 4-triazole, benzotriazole, 1,2, 3-oxadiazole, 1,2, 4-oxadiazole, 1,2, 5-oxadiazole, 1,3, 4-oxadiazole, 1,2, 3-thiadiazole, 1,2, 4-thiadiazole, 1,2, 5-thiadiazole, 1,3, 4-thiadiazole, 1,3, 5-triazine, 1,2, 4-triazine, 1,2, 3-triazine, tetrazole, 1,2,4, 5-tetrazine, 1,2,3, 4-tetrazine, 1,2,3, 5-tetrazine, purine, pteridine, indolizine, or benzothiadiazole. For the purposes of the present invention, C2-C10 aryl or heteroaryl is understood to mean, in particular, biphenylene, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, tetrahydropyrene and cis-or trans-indenofluorene, in addition to the abovementioned aryl and heteroaryl groups.
In one embodiment, M is selected from iridium, gold, platinum, or palladium; in one embodiment, M is selected from iridium.
Ir is particularly preferably used as the central metal M of the above-mentioned organic transition metal complex from the viewpoint of heavy atom effect. This is because iridium is chemically stable and has a significant heavy atom effect to obtain high luminous efficiency.
In one embodiment, Ar1Independently from each other: a substituted or unsubstituted aromatic group having 5 to 10 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms, or a substituted or unsubstituted non-aromatic ring system having 5 to 10 ring atoms.
In one embodiment, Ar1Independently from each other: substituted or unsubstituted aromatic radicals having 6 to 10 ring atoms orSubstituted or unsubstituted heteroaromatic groups having 6 to 10 ring atoms. In one embodiment, Ar1Independently from each other: substituted or unsubstituted heteroaromatic groups having 6 to 10 ring atoms.
Preferably, formula (1) is selected from formula (2-1) or formula (2-2):
Figure BDA0002307000190000031
further, Ar3、Ar4Independently selected from substituted or unsubstituted aromatic groups having 5 to 6 ring atoms or substituted or unsubstituted heteroaromatic groups having 5 to 6 ring atoms.
In one embodiment, Ar3、Ar4At least one of them is selected from substituted or unsubstituted aromatic or heteroaromatic groups having 6 ring atoms.
In one embodiment, Ar3、Ar4At least one of them is selected from substituted or unsubstituted heteroaromatic groups having 5 ring atoms.
In one embodiment, Ar3、Ar4Are each selected from substituted or unsubstituted heteroaromatic groups having 5 ring atoms.
Specifically, Ar3、Ar4Independently selected from the group consisting of:
Figure BDA0002307000190000032
y is selected from CR2R3、NR2、O、S、SiR2R3Or Se;
v is selected from CR4Or N or C; at least two adjacent V are selected from C and are linking sites;
R2-R4selected from the group consisting of hydrogen, deuterium, halogen, linear alkanes having 1 to 30 carbon atoms, branched alkanes having 1 to 30 carbon atoms, linear alkenes having 1 to 30 carbon atoms, branched alkenes having 1 to 30 carbon atoms, alkane ethers having 1 to 30 carbon atoms, aromatic groups havingA heteroaromatic group having 1 to 30 carbon atoms or a non-aromatic ring system having 1 to 30 carbon atoms;
in one embodiment, Ar3Is selected from
Figure BDA0002307000190000041
In one embodiment, Ar3Is selected from
Figure BDA0002307000190000042
In one embodiment, Ar4Is selected from
Figure BDA0002307000190000043
In one embodiment, Ar4Is selected from
Figure BDA0002307000190000044
Further, the air conditioner is provided with a fan,
Figure BDA0002307000190000045
selected from any one of structures (A-1) to (A-4):
Figure BDA0002307000190000046
wherein: v, Y is as defined above, and denotes the attachment site.
In a preferred embodiment of the present invention,
Figure BDA0002307000190000047
is selected from (A-1) or (A-2). In a preferred embodiment of the present invention,
Figure BDA0002307000190000048
is selected from (A-1).
In a preferred embodiment, at least one Y in (A-1) or (A-2) is selected from NR2。
In a preferred embodiment, one Y in (A-1) or (A-2) is selected from NR2And the other Y is selected from CR2R3、O、S、SiR2R3Or Se.
Preferably, formula (1) is selected from the following general formulae:
Figure BDA0002307000190000049
in one embodiment, Ar is defined herein1Selected from the group consisting of:
Figure BDA00023070001900000410
wherein:
Y1selected from the group consisting of CR5R6、NR5、O、S、SiR5R6Or Se;
X1selected from the group consisting of CR5Or N or C; at least two adjacent V are selected from C and are linking sites; preferably, at least one X1Is selected from N;
R5-R6selected from the group consisting of hydrogen, deuterium, halogen, linear alkanes having 1 to 30 carbon atoms, branched alkanes having 1 to 30 carbon atoms, linear alkenes having 1 to 30 carbon atoms, branched alkenes having 1 to 30 carbon atoms, alkane ethers having 1 to 30 carbon atoms, aromatic groups having 1 to 30 carbon atoms, heteroaromatic groups having 1 to 30 carbon atoms or non-aromatic ring systems having 1 to 30 carbon atoms.
Preferably, Ar1Selected from the group consisting of:
Figure BDA0002307000190000051
further, Ar1A heteroaromatic group selected from:
Figure BDA0002307000190000052
in a more preferred embodiment, Ar1Selected from the following general formulae:
Figure BDA0002307000190000053
wherein: # denotes linkage to Ar2The attachment site of (a); m has the same meaning as described above.
Preferably, X1Selected from the group consisting of CR5More preferably, R5Is selected from H.
In one embodiment, formula (1) is selected from any of the general formulas (B-1) to (B-36):
Figure BDA0002307000190000054
Figure BDA0002307000190000061
in a more preferred embodiment, the organic transition metal complex according to the invention, L in formula (1) is a monoanionic bidentate chelating ligand, which is preferably selected from, but not limited to, the following structures:
Figure BDA0002307000190000071
wherein:
Y1selected from the group consisting of CR5R6、NR5、O、S、SiR5R6Or Se;
X1selected from the group consisting of CR5Or N or C; at least two adjacent V are selected from C and are linking sites;
R5-R6selected from the group consisting of hydrogen, deuterium, halogen, linear alkanes having 1 to 30 carbon atoms, branched alkanes having 1 to 30 carbon atoms, linear alkenes having 1 to 30 carbon atoms, branched alkenes having 1 to 30 carbon atoms, alkane ethers having 1 to 30 carbon atoms, aromatic groups having 1 to 30 carbon atoms, heteroaromatic groups having 1 to 30 carbon atoms or non-aromatic ring systems having 1 to 30 carbon atoms.
Further, L is selected from the group consisting of:
Figure BDA0002307000190000072
wherein the H atom on the ring may be further substituted by R5And (4) substitution.
In a preferred embodiment, formula (1) is selected from (3-1) or (3-2):
Figure BDA0002307000190000073
more preferably, formula (3-1) is at X1Are all selected from CR5。
Specific examples of suitable organometallic complexes according to the invention in which M is selected from Ir are given below, without being restricted thereto:
Figure BDA0002307000190000081
Figure BDA0002307000190000091
Figure BDA0002307000190000101
Figure BDA0002307000190000111
Figure BDA0002307000190000121
Figure BDA0002307000190000131
in one embodiment, when M is selected from Au, the structural formulas (Au-001) to (Au-245) are the same as those of (Ir-001) to (Ir-245), except that M is changed from Ir to M is selected from Au.
In one embodiment, when M is selected from Pt, (Pt-001) to (Pt-245) have the same structural formula as (Ir-001) to (Ir-245), except that M is changed from Ir to M is selected from Pt; and m-2 in the structural formulae (Ir-001) to (Ir-245) is modified to m-1 or n-2 is modified to n-1, or n-3 is modified to n-2.
In one embodiment, when M is selected from Ru, the structural formula of (Ru-001) to (Ru-245) is the same as that of (Ir-001) to (Ir-245), except that the M is changed from Ir to Ru; and m-2 in the structural formulae (Ir-001) to (Ir-245) is modified to m-1 or n-2 is modified to n-1, or n-3 is modified to n-2.
In one embodiment, when M is selected from Cu, the structural formulas (Cu-001) to (Cu-245) are the same as those of (Ir-001) to (Ir-245), except that M is changed from Ir to M is selected from Cu; and m-2 in the structural formulae (Ir-001) -to (Ir-245) is modified to m-1 or n-2 is modified to n-1, or n-3 is modified to n-2.
In one embodiment, when M is selected from Zn, (Zn-001) to (Zn-245) have the same structural formula as (Ir-001) to (Ir-245), except that M is changed from Ir to M is selected from Zn; and m-2 in the structural formulae (Ir-001) to (Ir-245) is modified to m-1 or n-2 is modified to n-1, or n-3 is modified to n-2.
In one embodiment, when M is selected from Pd, (Pd-001) to (Pd-245) have the same structural formula as (Ir-001) to (Ir-245), except that M is changed from Ir to Pd; and m-2 in the structural formulae (Ir-001) to (Ir-245) is modified to m-1 or n-2 is modified to n-1, or n-3 is modified to n-2.
The other divalent metal structural formulas are as described above.
When M is selected from monovalent metals, the difference is that n is 1 and M is 0.
The organic transition metal complex can be used as a functional material for electronic devices. Organic functional materials include, but are 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 material (Emitter), or a Host material (Host).
In a particularly preferred embodiment, the organic transition metal complexes according to the invention are luminescent materials which emit light at a wavelength of between 300 and 1000nm, preferably between 350 and 900nm, more preferably between 400 and 800 nm. Luminescence as used herein refers to photoluminescence or electroluminescence.
In certain preferred embodiments, the organic transition metal complexes according to the invention have a photoluminescent or electroluminescent efficiency of 30% or more, preferably 40% or more, more preferably 50% or more, most preferably 60% or more.
In a particularly preferred embodiment, the organic transition metal complexes according to the invention are used as phosphorescent guests.
As a phosphorescent guest material, it must have an appropriate triplet energy level, i.e., T1. In certain embodiments, the compounds according to the invention, T thereof1More preferably, it is not less than 2.0eV, still more preferably not less than 2.2eV, still more preferably not less than 2.4eV, particularly preferably not less than 2.6 eV.
Good thermal stability is desired as a functional material. In general, the organic transition metal complexes according to the invention have a glass transition temperature Tg of 100 ℃ or higher, in a preferred embodiment 120 ℃ or higher, in a more preferred embodiment 140 ℃ or higher, in a more preferred embodiment 160 ℃ or higher, and in a most preferred embodiment 180 ℃ or higher.
In certain preferred embodiments, the organic transition metal complexes according to the invention ((HOMO- (HOMO-1)) are ≧ 0.2eV, preferably ≧ 0.25eV, more preferably ≧ 0.3eV, more preferably ≧ 0.35eV, very preferably ≧ 0.4eV, most preferably ≧ 0.45 eV.
In further preferred embodiments, the organic transition metal complexes according to the invention (((LUMO +1) -LUMO) are ≥ 0.15eV, preferably ≥ 0.20eV, more preferably ≥ 0.25eV, even more preferably ≥ 0.30eV, most preferably ≥ 0.35 eV.
The present invention still further relates to a polymer having at least one repeating unit comprising the structure represented by the organic transition metal complex.
In a preferred embodiment, the polymer is synthesized by a method selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD-and ULLMAN.
In a preferred embodiment, the polymers according to the invention have a glass transition temperature (Tg) of 100 ℃ or higher, preferably 120 ℃ or higher, more preferably 140 ℃ or higher, still more preferably 160 ℃ or higher, most preferably 180 ℃ or higher.
In a preferred embodiment, the polymers according to the invention preferably have a molecular weight distribution (PDI) in the range from 1 to 5; more preferably 1 to 4; more preferably 1 to 3, more preferably 1 to 2, and most preferably 1 to 1.5.
In a preferred embodiment, the polymers according to the invention preferably have a weight-average molecular weight (Mw) ranging from 1 to 100 ten thousand; more preferably 5 to 50 ten thousand; more preferably 10 to 40 ten thousand, still more preferably 15 to 30 ten thousand, and most preferably 20 to 25 ten thousand.
In certain embodiments, the polymer according to the present invention is a non-conjugated polymer. Preference is given to a non-conjugated polymer in which the structural unit of the organic transition metal complex is contained as a repeating unit in a side chain.
The invention also provides a mixture, which is characterized by comprising at least one organic transition metal complex or polymer and at least another organic functional material, wherein the at least another organic functional material can be 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 luminescent material (Emitter), a Host material (Host) or an organic dye. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference.
In certain embodiments, the organic transition metal complex is present in the mixture according to the invention in an amount of from 0.01 to 30 wt.%, preferably from 0.5 to 20 wt.%, more preferably from 2 to 15 wt.%, most preferably from 5 to 15 wt.%.
In a preferred embodiment, the mixtures according to the invention comprise an organic transition metal complex or polymer according to the invention and a triplet host material.
In a further preferred embodiment, the mixtures according to the invention comprise an organic transition metal complex or polymer according to the invention, a triplet matrix material and a further triplet emitter.
In a further preferred embodiment, the mixtures according to the invention comprise an organic transition metal complex or polymer according to the invention and a thermally activated delayed fluorescence emitter (TADF).
In a further preferred embodiment, the mixtures according to the invention comprise an organic transition metal complex or polymer according to the invention, a triplet matrix material and a thermally activated delayed fluorescence light-emitting material (TADF).
Some more detailed descriptions of triplet host materials, triplet emitters and TADF materials are provided below (but not limited thereto).
1. Triplet Host material (Triplet Host):
examples of the triplet Host material are not particularly limited, and any metal complex or organic compound may be used as the Host as long as the triplet energy level thereof is higher than that of a light emitter, particularly a triplet light emitter or a phosphorescent light emitter, and examples of the metal complex which can be used as the triplet Host (Host) include, but are not limited to, the following general structures:
Figure BDA0002307000190000141
m3 is a metal; (Y)7-Y8) Is a bidentate ligand, Y7And Y8Independently selected from C, N, O, P or S; l is an ancillary ligand; m3 is an integer having a value from 1 to the maximum coordination number of the metal; in a preferred embodiment, metal complexes useful as triplet hosts
The compound has the following form:
Figure BDA0002307000190000142
(O-N) is a bidentate ligand wherein the metal is coordinated to both the O and N atoms, and m3 is an integer having a value from 1 up to the maximum coordination number for the metal;
in one embodiment, M3 may be selected from Ir and Pt.
Examples of the organic compound which can be a triplet host are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenylbenzene, benzofluorene; compounds containing aromatic heterocyclic groups, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, dibenzocarbazole, indolocarbazole, pyridine indole, pyrrole bipyridine, pyrazole, imidazole, triazoles, oxazole, thiazole, oxadiazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, oxazole, dibenzooxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuran pyridine, furopyridine, benzothiophene pyridine, thiophene pyridine, benzoselenophene pyridine, and selenophene benzodipyridine; groups having 2 to 10 ring structures, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, are bonded to each other directly or through at least one group selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic group. Wherein each Ar may be further substituted, and the substituents may be selected from the group consisting of hydrogen, deuterium, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.
In a preferred embodiment, the triplet host material may be selected from compounds comprising at least one of the following groups:
Figure BDA0002307000190000151
R1-R7has the same meaning as R1，X9Is selected from CR1R2Or NR1Y is selected from CR1R2Or NR1Or O or S, n2 is selected from any integer of 0-20, X1-X8Has the same meaning as X1，Ar1～Ar3Has the same meaning as Ar1。R1，X1，Ar1The meaning of (A) is as described above.
Examples of suitable triplet host materials are listed in the following table but are not limited to:
Figure BDA0002307000190000152
Figure BDA0002307000190000161
2. thermally activated delayed fluorescence luminescent material (TADF):
the traditional organic fluorescent material can only emit light by utilizing 25% singlet excitons formed by electric excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescence material enhances the intersystem crossing due to the strong spin-orbit coupling of the heavy atom center, the singlet excitons and the triplet excitons formed by the electric excitation can be effectively used for emitting light, so that the internal quantum efficiency of the device reaches 100 percent. However, the application of the phosphorescent material in the OLED is limited by the problems of high price, poor material stability, serious efficiency roll-off of the device and the like. The thermally activated delayed fluorescence emitting material is a third generation organic emitting material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (Δ Est), and triplet excitons may be converted to singlet excitons for emission by intersystem crossing. This can make full use of singlet excitons and triplet excitons formed upon electrical excitation. The quantum efficiency in the device can reach 100%. Meanwhile, the material has controllable structure, stable property, low price and no need of noble metal, and has wide application prospect in the field of OLED.
TADF materials need to have a small singlet-triplet level difference, preferably Δ Est <0.3eV, less preferably Δ Est <0.25eV, more preferably Δ Est <0.20eV, and most preferably Δ Est <0.1 eV. In a preferred embodiment, the TADF material has a relatively small Δ Est, and in another preferred embodiment, the TADF has a good fluorescence quantum efficiency. Some TADF luminescent materials can be found in the following patent documents: CN103483332(a), TW201309696(a), TW201309778(a), TW201343874(a), TW201350558(a), US20120217869(a1), WO2013133359(a1), WO2013154064(a1), Adachi, et.al.adv.mater, TW 20135084, Adachi, et.al.appl.lett. 98,2011,083302, Adachi, et.al.appl.phys.lett. 101,2012,093306, Adachi, et.al.chem.comm. 48,2012,11392, Adachi, et.al.nature photomonics, 6,2012,253, Adachi, et.al.nature,492,2012,234, Adachi, et.al.j.chem. 134,2012,14706, soochi, adachi.38, adachi.68, adachi.73, et.7, adachi.73, adv.38, adachi.73, et.8, adachi.t.7, adachi.t.t.7, adachi.7, adachi.t.t.t.638, adachi.t.t.t.t.t.t.
3. Triplet Emitter (Triplet Emitter)
Triplet emitters are also known as phosphorescent emitters. In a preferred embodiment, the triplet emitter is of the formula M4(L4)n4The metal complex of (1), wherein M4Is a metal atom, L4Each occurrence of which may be the same or different, is an organic ligand which is bonded or coordinately bound to the metal atom M via one or more positions4Upper, n4Is an integer greater than 1, preferably 1,2,3,4, 5 or 6. Optionally, the metal complexes are coupled to a polymer through one or more sites, preferably through organic ligands.
In a preferred embodiment, the metal atom M4From the group of transition metals or lanthanides or actinides, preference is given to Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, particular preference to Os, Ir, Ru, Rh, Re, Pd, Au or Pt.
Preferably, the triplet emitter comprises a chelating ligand, i.e. a ligand, which coordinates to the metal via at least two binding sites, particularly preferably the triplet emitter comprises two or three identical or different bidentate or polydentate ligands. Chelating ligands are advantageous for increasing the stability of the metal complex.
Examples of organic ligands may be selected from phenylpyridine derivatives, 7, 8-benzoquinoline derivatives, 2 (2-thienyl) pyridine derivatives, 2 (1-naphthyl) pyridine derivatives, or 2-phenylquinoline derivatives. All of these organic ligands may be substituted, for example, with fluorine-containing or trifluoromethyl groups. The ancillary ligand may preferably be selected from acetone acetate or picric acid.
In a preferred embodiment, the metal complexes which can be used as triplet emitters are of the form:
Figure BDA0002307000190000171
wherein M is4Is a metal selected from the transition metals or the lanthanides or actinides, particularly preferably Ir, Pt or Au;
Ar1each occurrence of which may be the same or different, is a cyclic group containing at least one donor atom, i.e., an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which the cyclic group is coordinately bound to the metal; ar (Ar)2Each occurrence, which may be the same or different, is a cyclic group containing at least one C atom through which the cyclic group is attached to the metal; ar (Ar)1And Ar2Linked together by a covalent bond, which may each carry one or more substituent groups, which may in turn be linked together by substituent groups; l', which may be the same or different at each occurrence, is a bidentate chelating ancillary ligand, preferably a monoanionic bidentate chelating ligand; q1 may be 0, 1,2 or 3, preferably 2 or 3; q2 may be 0, 1,2 or 3, preferably 1 or 0.
Examples of materials and their use for some triplet emitters can be found in WO200070655, WO 200141512, WO 200202714, WO 200202714, EP 200202714, EP 1191612, EP1191614, WO 200202714, WO 200202714, US 200202714, WO2010015307, WO 200202714, WO 200202714, WO 200202714, WO2010099852, WO 200202714, US 200202714A 200202714, US 200202714A 200202714, Baldo, Thompson et al Nature, (750) 36753, US 200202714A 200202714, US 200202714A 200202714, Adachi et al Appys.Lett.78 (2001), 1622-Buchner 1624, J.Kido et al, Appl. Phys.Lett.65 (364), Kido et al, WO 200202714, WO 200202714, US 200202714A 200202714, US 200202714A 200202714, US 200202714A 200202714, US 200202714, US 200202714A 200202714, US 200202714A 200202714, US 200202714, US 200202714, US 200202714A 200202714, US 200202714A 200202714, US 200202714A 200202714, WO 363636363636363672A 3636363636363636363636363636363672A 3636, WO2009118087a1, WO 2013107487a1, WO 2013094620a1, WO 2013174471a1, WO 2014031977a1, WO 2014112450a1, WO 2014007565a1, WO 2014038456a1, WO 2014024131a1, WO2014008982a1, WO2014023377a 1. The entire contents of the above listed patent documents and literature are hereby incorporated by reference.
Some examples of suitable triplet emitters are listed in the following table:
Figure BDA0002307000190000172
Figure BDA0002307000190000181
it is an object of the present invention to provide a material solution for evaporation type OLEDs.
In certain embodiments, the organic transition metal complexes according to the invention have a molecular weight of 1200g/mol or less, preferably 1100g/mol or less, very preferably 1000g/mol or less, more preferably 950g/mol or less, and most preferably 900g/mol or less.
It is another object of the present invention to provide a material solution for printing OLEDs.
In certain embodiments, the organic transition metal complexes according to the invention have a molecular weight of 800g/mol or more, preferably 900g/mol or more, very preferably 1000g/mol or more, more preferably 1100g/mol or more, most preferably 1200g/mol or more.
In further embodiments, the organic transition metal complexes according to the invention have a solubility in toluene of 2mg/ml or more, preferably 3mg/ml or more, more preferably 4mg/ml or more, most preferably 5mg/ml or more at 25 ℃.
The invention also relates to a composition comprising at least one organic transition metal complex or polymer or mixture as described above, and at least one organic solvent; the at least one organic solvent is selected from aromatic, heteroaromatic, ester, aromatic ketone, aromatic ether, aliphatic ketone, aliphatic ether, alicyclic, olefinic compound, boric acid ester or phosphoric acid ester compound, or a mixture of two or more solvents.
In a preferred embodiment, a composition according to the invention, the organic solvent is selected from one or a mixture of two or more of aromatic and heteroaromatic-based solvents.
Examples of aromatic or heteroaromatic-based solvents suitable for the present invention include, but are not limited to, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 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-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, 1, 2-dimethylquinoline, 2-benzoic acid, 2-isopropylquinoline, 2-benzoic acid, 2-ethyl benzoate, and the like.
Examples of aromatic ketone-based solvents suitable for the present invention are, but not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, and the like.
Examples of aromatic ether-based solvents suitable for the present invention are, but not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxan, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylphenetole, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, methyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether.
In some preferred embodiments, the at least one organic solvent may be selected from: aliphatic ketones such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, fenchylone, phorone, isophorone, di-n-amyl ketone, etc.; or aliphatic ethers such as 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, tetraethylene glycol dimethyl ether, and the like.
In other preferred embodiments, the at least one organic solvent may be selected from ester-based solvents, such as alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like, in accordance with the compositions of the present invention. Octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate are particularly preferred.
The organic solvent may be used alone or as a mixture of two or more organic solvents.
In certain preferred embodiments, a composition according to the present invention comprises at least one organic transition metal complex or polymer or mixture as described above and at least one organic solvent, and may further comprise another organic solvent. Examples of another organic solvent include, but are not limited to: methanol, ethanol, 2-methoxyethanol, methylene chloride, 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, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene, or mixtures thereof.
In some preferred embodiments, organic solvents particularly suitable for the present invention are those having Hansen (Hansen) solubility parameters within the following ranges:
δd(dispersion force) of 17.0 to 23.2MPa1/2In particular in the range of 18.5 to 21.0MPa1/2A range of (d);
δp(polar force) is 0.2 to 12.5MPa1/2In particular in the range of 2.0 to 6.0MPa1/2A range of (d);
δh(hydrogen bonding force) of 0.9 to 14.2MPa1/2In particular in the range of 2.0 to 6.0MPa1/2The range of (1).
The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably equal to or more than 180 ℃; more preferably more than or equal to 200 ℃; more preferably more than or equal to 250 ℃; most preferably more than or equal to 275 ℃ or more than or equal to 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads. The organic solvent may be evaporated from the solvent system to form a thin film comprising the functional material.
In a preferred embodiment, the composition according to the invention is a solution.
In another preferred embodiment, the composition according to the invention is a suspension.
The compositions of the embodiments of the present invention may comprise from 0.01 to 10 wt%, preferably from 0.1 to 15 wt%, more preferably from 0.2 to 5 wt%, most preferably from 0.25 to 3 wt%, of an organic transition metal complex or polymer or mixture according to the present invention.
The invention also relates to the use of said composition as a coating or printing ink for the production of organic electronic devices, particularly preferably by a printing or coating production process.
Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, jet Printing (Nozzle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, offset Printing, flexographic Printing, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Gravure printing, jet printing and ink jet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like. For details on the printing technology and its requirements concerning the solutions, such as solvent and concentration, viscosity, etc., reference is made to the Handbook of Print Media, technology and production Methods, published by Helmut Kipphan, ISBN 3-540-67326-1.
The present invention also provides a use of the Organic transition metal complex, polymer, mixture or composition as described above in an Organic electronic device, which may be selected from, but not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light emitting field effect transistors (efets), Organic lasers, Organic spintronic devices, Organic sensors, and Organic plasmon emitting diodes (Organic plasmon emitting diodes), etc., and particularly preferably is an OLED. In the embodiment of the present invention, the organic transition metal complex or the polymer is preferably used for a light emitting layer of an OLED device.
The invention further relates to an organic electronic component comprising at least one organic transition metal complex, polymer or mixture as described above or prepared from a composition as described above. Generally, such organic electronic devices comprise at least a cathode, an anode and a functional layer located between the cathode and the anode, wherein the functional layer comprises at least one organic mixture as described above. The Organic electronic device can be selected from, but not limited to, Organic Light Emitting Diode (OLED), Organic photovoltaic cell (OPV), Organic light emitting cell (OLEEC), Organic Field Effect Transistor (OFET), Organic light emitting field effect transistor (fet), Organic laser, Organic spintronic device, Organic sensor, Organic plasmon emitting Diode (Organic plasmon emitting Diode), and the like, and particularly preferred is Organic electroluminescent device such as OLED, OLEEC, Organic light emitting field effect transistor.
In certain particularly preferred embodiments, the organic electronic device comprises a light-emitting layer comprising an organic transition metal complex or polymer or mixture as described above or prepared from a composition as described above.
In the above-mentioned light emitting device, especially an OLED, it comprises a substrate, an anode, at least one light emitting layer, and a cathode.
The substrate may be opaque or transparent. 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, p 2606. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).
The anode may comprise a conductive metal, metal oxide or conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or an emission layer. 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 0.2 eV. 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 invention.
The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. 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 of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2Al, 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 light-emitting device according to the present invention emits light at a wavelength of 300 to 1000nm, preferably 350 to 900nm, more preferably 400 to 800 nm.
The invention also relates to the use of the organic electronic device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.
The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
1. Organic transition metal complex and energy structure thereof
Figure BDA0002307000190000201
The energy level of the organic transition metal complex can be obtained by quantum calculation, for example, by using TD-DFT (time-density functional theory) through Gaussian03W (Gaussian Inc.), and a specific simulation method can be seen in WO 2011141110. Firstly, a semi-empirical method of 'group State/Hartree-Fock/Default Spin/LanL2 MB' (Charge 0/SpinSinglet) is used for optimizing the molecular geometrical structure, and then the energy structure of the organic molecule is calculated by a TD-DFT (time-density functional theory) method to obtain 'TD-SCF/DFT/Default Spin/B3PW91/gen gain ═ connection property pseudo ═ lan 2' (Charge 0/Spin Singlet). The HOMO and LUMO energy levels were calculated according to the following calibration formula, and S1 and T1 were used directly.
HOMO(eV)＝((HOMO(Gaussian)×27.212)-0.9899)/1.1206
LUMO(eV)＝((LUMO(Gaussian)×27.212)-2.0041)/1.385
Where HOMO (G) and LUMO (G) are direct calculations of Gaussian03W in Hartree. The results are shown in table one:
watch 1
Figure BDA0002307000190000202
Figure BDA0002307000190000211
2. Synthesis of organic transition metal complexes
Synthesis example 1: synthesis complex (Ir-003)
Synthesis intermediate (Ir-003-a):
Figure BDA0002307000190000212
placing 3-bromosalicylaldehyde (10g,1eq), carbon tetrabromide (50g,3eq) and triphenylphosphine (79g,6eq) in a dry double-mouth bottle, adding 500mL dichloromethane into an ice bath at 0 ℃ to prepare a solution, reacting for 0.5 hour, adding 44mL triethylamine, reacting for 2 hours at normal temperature, performing spin-drying after the reaction is completed, separating the solution by dichloromethane and water, drying by magnesium sulfate, performing spin-drying, and performing separation and purification by a silica gel chromatographic column. A solid was obtained as intermediate (Ir-003-a) in 98% yield.
Synthesis of intermediate (Ir-003-b):
Figure BDA0002307000190000213
after placing the intermediate (Ir-003-a) (20g,1eq), potassium phosphate (31g,2eq), and cuprous iodide (0.68g,0.05eq) in a dry two-necked flask, 500mL of tetrahydrofuran was added as a solution, and the mixture was stirred at 80 ℃ for 8 hours, cooled to room temperature, spun dry after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate, spun dry, and then purified by silica gel chromatography. The solid intermediate (Ir-003-b) was obtained in 80% yield.
Synthesis of intermediate (Ir-003-c):
Figure BDA0002307000190000214
placing 2-nitrobenzene in a dry double-mouth bottleBoric acid (27.8g,0.9eq), intermediate (Ir-003-b) (40g,1eq), Pd (PPh)3)4(8g,0.05eq) and potassium carbonate (80g,4eq), then 500mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the mixture was stirred at 80 ℃ for reaction for 10 hours, the reaction mixture was cooled to room temperature, after completion of the reaction, the reaction mixture was spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and then spin-dried, and then subjected to separation and purification by a silica gel chromatography column. The solid intermediate (Ir-003-c) was obtained in 85% yield.
Synthesis of intermediate (Ir-003-d):
Figure BDA0002307000190000215
place pinacol diboron (24.15g,1.5eq), intermediate (Ir-003-c) (20g,1eq), Pd (dppf) in a dry, two-necked flask2Cl2(2.3g,0.05eq) and potassium acetate (24g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 100 ℃ for 12 hours, the mixture was cooled to room temperature, after the reaction was completed, the mixture was spin-dried, separated by dichloromethane and water, dried over magnesium sulfate and then spin-dried, and then separated and purified by a silica gel column chromatography. The solid intermediate (Ir-003-d) was obtained in 78% yield.
Synthesis of intermediate (Ir-003-e):
Figure BDA0002307000190000216
in a dry two-necked flask was placed 2-bromopyridine (5.19g,1.2eq), intermediate (Ir-003-d) (10g,1eq), Pd (PPh)3)4(1.58g,0.05eq), potassium carbonate (15.12g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 95 ℃ for 12 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and spin-dried, and then subjected to separation and purification by a silica gel chromatography column. The solid intermediate (Ir-003-e) was obtained in 85% yield.
Synthesis of intermediate (Ir-003-f):
Figure BDA0002307000190000221
after placing the intermediate (Ir-003-e) (5g,1eq) and triphenylphosphine (15.8g,5eq) in a dry two-necked flask, 150mL of 1, 2-dichlorobenzene was added as a solution, and the mixture was stirred at 160 ℃ for 12 hours, cooled to room temperature, dried after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate, dried again, and then purified by separation with a silica gel column. The solid intermediate (Ir-003-f) was obtained in 95% yield.
Synthesis of intermediate (Ir-003-g):
Figure BDA0002307000190000222
after placing the intermediate (Ir-003-f) (5g,1eq), sodium hydride (1.3g,2eq) and methyl iodide (2.8g,1.2eq) in a dry two-necked flask, 50mL of tetrahydrofuran was added as a solution, and the mixture was stirred at 80 ℃ for 6 hours, cooled to room temperature, and after completion of the reaction, the mixture was dried by spinning, separated from dichloromethane and water, dried over magnesium sulfate and then dried, and then purified by separation with a silica gel column. A solid intermediate (Ir-003-g) was obtained in 90% yield.
Synthesis of intermediate (Ir-003-h):
Figure BDA0002307000190000223
putting 2-phenylpyridine (8.1g,3eq) into a single-neck flask, adding iridium trichloride (5.2g,1eq), adding a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of water, heating to 110 ℃, reacting for 12 hours, cooling to room temperature, pouring into an aqueous solution of sodium chloride, filtering, and drying to obtain an intermediate (Ir-003-h) with the yield of 60%.
Synthesis of Complex (Ir-003):
Figure BDA0002307000190000224
putting the intermediate (Ir-003-h) (7.6g,1eq) into a single-mouth bottle, adding silver trifluoromethanesulfonate (5.4g,3eq), adding a mixed solution of 300mL of dichloromethane and 100mL of methanol, stirring at 60 ℃, reacting for 6 hours, filtering and drying. Then, the obtained solid was mixed with intermediate (Ir-003-g) (6.34g,3eq), a mixed solution of 250mL of ethanol and 250mL of methanol was added, the reaction was stirred at room temperature for 14 hours, and the mixture was extracted with methylene chloride, spin-dried, then subjected to separation purification using a silica gel column, and then recrystallized to obtain a yellow solid complex (Ir-003) in 40% yield.
Synthesis example 2: synthetic complex (Ir-013)
Synthesis intermediate (Ir-013-a):
Figure BDA0002307000190000225
placing 2-bromo-6-hydroxybenzaldehyde (10g,1eq), carbon tetrabromide (50g,3eq) and triphenylphosphine (79g,6eq) in a dry double-mouth bottle, adding 500mL dichloromethane as a solution in an ice bath at 0 ℃, reacting for 0.5 hour, adding 44mL triethylamine, reacting for 2 hours at normal temperature, performing spin-drying after the reaction is completed, separating liquid with dichloromethane and water, drying with magnesium sulfate, performing spin-drying, and performing separation and purification by using a silica gel chromatographic column. A solid was obtained as intermediate (Ir-013-a) in 90% yield.
Synthesis of intermediate (Ir-013-b):
Figure BDA0002307000190000226
in a dry two-necked flask, the intermediate (Ir-013-a) (20g,1eq), potassium phosphate (31g,2eq), and cuprous iodide (0.68g,0.05eq) were placed, and then 500mL of tetrahydrofuran was added as a solution, stirred at 80 ℃ for reaction for 8 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate, spin-dried, and then separated and purified by silica gel chromatography. A solid intermediate (Ir-013-b) was obtained in 85% yield.
Synthesis intermediate (Ir-013-c):
Figure BDA0002307000190000227
placing 2-nitrophenylboronic acid (27.8g,0.9 eq.) in a dry two-neck flask,Intermediate (Ir-013-b) (40g,1eq), Pd (PPh)3)4(8g,0.05eq) and potassium carbonate (80g,4eq), then 500mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the mixture was stirred at 80 ℃ for reaction for 10 hours, the reaction mixture was cooled to room temperature, after completion of the reaction, the reaction mixture was spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and then spin-dried, and then subjected to separation and purification by a silica gel chromatography column. A solid intermediate (Ir-013-c) was obtained in 90% yield.
Synthesis intermediate (Ir-013-d):
Figure BDA0002307000190000231
place pinacol diboron (24.15g,1.5eq), intermediate (Ir-013-c) (20g,1eq), Pd (dppf) in a dry, two-necked flask2Cl2(2.3g,0.05eq) and potassium acetate (24g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 100 ℃ for 12 hours, the mixture was cooled to room temperature, after the reaction was completed, the mixture was spin-dried, separated by dichloromethane and water, dried over magnesium sulfate and then spin-dried, and then separated and purified by a silica gel column chromatography. A solid intermediate (Ir-013-d) was obtained in 65% yield.
Synthesis of intermediate (Ir-013-e):
Figure BDA0002307000190000232
in a dry two-necked flask was placed 2-bromopyridine (5.19g,1.2eq), intermediate (Ir-013-d) (10g,1eq), Pd (PPh)3)4(1.58g,0.05eq), potassium carbonate (15.12g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 95 ℃ for 12 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and spin-dried, and then subjected to separation and purification by a silica gel chromatography column. A solid intermediate (Ir-013-e) was obtained in 75% yield.
Synthesis of intermediate (Ir-013-f):
Figure BDA0002307000190000233
after placing the intermediate (Ir-013-e) (5g,1eq) and triphenylphosphine (15.8g,5eq) in a dry two-necked flask, 150mL of 1, 2-dichlorobenzene was added as a solution, the reaction was stirred at 160 ℃ for 12 hours, cooled to room temperature, dried after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate and then dried, and then separated and purified by silica gel chromatography. A solid intermediate (Ir-013-f) was obtained in 80% yield.
Synthesis of intermediate (Ir-013-g):
Figure BDA0002307000190000234
after placing the intermediate (Ir-013-f) (5g,1eq), sodium hydride (1.3g,2eq) and methyl iodide (2.8g,1.2eq) in a dry two-necked flask, 50mL of tetrahydrofuran was added as a solution, and the mixture was stirred at 80 ℃ for 6 hours, cooled to room temperature, and after completion of the reaction, the mixture was dried by spinning, separated from dichloromethane and water, dried over magnesium sulfate and then dried, and then separated and purified by a silica gel column chromatography. A solid intermediate (Ir-013-g) was obtained in 95% yield. Synthesis of Complex (Ir-013):
Figure BDA0002307000190000235
putting the intermediate (Ir-013-g) (9.99g,5eq), iridium trichloride (2.00g,1eq) and potassium carbonate (4.62g,5eq) into a single-mouth bottle, adding 250mL of glycerol as a solvent, and heating to 300 ℃ for reaction for 24 hours. After completion of the reaction, it was cooled to room temperature, 2000mL of water was added to precipitate a yellow solid, which was filtered and washed with water and methanol to obtain a yellow solid complex (Ir-013) in 60% yield after recrystallization.
Synthetic example 3: synthesis complex (Ir-018)
Synthesis of intermediate (Ir-018-a):
Figure BDA0002307000190000236
4-bromo-2-hydroxybenzaldehyde (10g,1eq), carbon tetrabromide (50g,3eq) and triphenylphosphine (79g,6eq) are placed in a dry double-neck flask, then 500mL of dichloromethane are added as a solution in an ice bath at 0 ℃, after 0.5 hour of reaction, 44mL of triethylamine is added for further 2 hours at normal temperature, after completion of the reaction, the solution is spun dry, separated by dichloromethane and water, dried with magnesium sulfate and then spun dry, and then separated and purified by a silica gel chromatography column. A solid was obtained as intermediate (Ir-018-a) in 96% yield.
Synthesis of intermediate (Ir-018-b):
Figure BDA0002307000190000241
after placing the intermediate (Ir-018-a) (20g,1eq), potassium phosphate (31g,2eq), and cuprous iodide (0.68g,0.05eq) in a dry double-neck flask, 500mL of tetrahydrofuran was added as a solution, and the mixture was stirred at 80 ℃ for 8 hours, cooled to room temperature, spun dry after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate, spun dry, and then separated and purified by a silica gel column chromatography. A solid intermediate (Ir-018-b) was obtained in 88% yield.
Synthesis of intermediate (Ir-018-c):
Figure BDA0002307000190000242
in a dry two-necked flask was placed 2-nitrophenylboronic acid (27.8g,0.9eq), intermediate (Ir-018-b) (40g,1eq), Pd (PPh)3)4(8g,0.05eq) and potassium carbonate (80g,4eq), then 500mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the mixture was stirred at 80 ℃ for reaction for 10 hours, the reaction mixture was cooled to room temperature, after completion of the reaction, the reaction mixture was spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and then spin-dried, and then subjected to separation and purification by a silica gel chromatography column. A solid intermediate (Ir-018-c) was obtained in 93% yield.
Synthesis of intermediate (Ir-018-d):
Figure BDA0002307000190000243
at one endPut pinacol diboron (24.15g,1.5eq), intermediate (Ir-018-c) (20g,1eq), Pd (dppf) in a dry two-necked flask2Cl2(2.3g,0.05eq) and potassium acetate (24g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 100 ℃ for 12 hours, the mixture was cooled to room temperature, after the reaction was completed, the mixture was spin-dried, separated by dichloromethane and water, dried over magnesium sulfate and then spin-dried, and then separated and purified by a silica gel column chromatography. A solid intermediate (Ir-018-d) was obtained in 72% yield.
Synthesis of intermediate (Ir-018-e):
Figure BDA0002307000190000244
in a dry two-necked flask was placed 2-bromopyridine (5.19g,1.2eq), intermediate (Ir-018-d) (10g,1eq), Pd (PPh)3)4(1.58g,0.05eq), potassium carbonate (15.12g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 95 ℃ for 12 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and spin-dried, and then subjected to separation and purification by a silica gel chromatography column. A solid intermediate (Ir-018-e) was obtained in 75% yield.
Synthesis of intermediate (Ir-018-f):
Figure BDA0002307000190000245
after placing the intermediate (Ir-018-e) (5g,1eq) and triphenylphosphine (15.8g,5eq) in a dry two-necked flask, 150mL of 1, 2-dichlorobenzene was added as a solution, and the mixture was stirred at 160 ℃ for 12 hours, cooled to room temperature, dried after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate, dried again, and then purified by separation with a silica gel column. A solid intermediate (Ir-018-f) was obtained in 87% yield.
Synthesis of intermediate (Ir-018-g):
Figure BDA0002307000190000246
after placing the intermediate (Ir-018-f) (5g,1eq), sodium hydride (1.3g,2eq) and methyl iodide (2.8g,1.2eq) in a dry double-necked flask, 50mL of tetrahydrofuran was added as a solution, and the mixture was stirred at 80 ℃ for 6 hours, cooled to room temperature, and after completion of the reaction, the mixture was dried by spinning, separated from dichloromethane and water, dried over magnesium sulfate and then dried, and then separated and purified by a silica gel column chromatography. A solid intermediate (Ir-018-g) was obtained in 84% yield.
Synthesis of intermediate (Ir-018-h):
Figure BDA0002307000190000247
putting 2-phenylpyridine (14.99g,3eq) into a single-neck bottle, adding iridium trichloride (5g,1eq), adding a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of water, heating to 110 ℃, reacting for 12 hours, cooling to room temperature, pouring into an aqueous solution of sodium chloride, filtering, and drying to obtain an intermediate (Ir-018-h) with a yield of 58%.
Synthesis of Complex (Ir-018):
Figure BDA0002307000190000251
putting the intermediate (Ir-018-h) (10g,1eq) into a single-mouth bottle, adding silver trifluoromethanesulfonate (4.68g,3eq), adding a mixed solution of 300mL of dichloromethane and 100mL of methanol, stirring at 60 ℃, reacting for 6 hours, filtering and drying. Then, the obtained solid was mixed with 2- (2-pyridine) -benzimidazole (3.56g,3eq), a mixed solution of 250mL of ethanol and 250mL of methanol was added, the reaction was stirred at room temperature for 14 hours, and the mixture was extracted with dichloromethane, spin-dried, separated and purified by a silica gel column chromatography, and then recrystallized to obtain a yellow solid complex (Ir-018) with a yield of 27%.
Synthetic example 4: synthetic complex (Ir-021)
Synthesis of intermediate (Ir-021-a):
Figure BDA0002307000190000252
in a dry two-necked flask, the intermediate (Ir-003-f) (10g,1eq), iodobenzene (10.18g, 1.5eq), cuprous iodide (3.19g,0.5eq), ethylenediamine (2.01g,1eq), and cesium carbonate (21.84g,2eq) were placed, then 100mL of tetrahydrofuran was added as a solution, stirred at 80 ℃ for 6 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried with magnesium sulfate, spin-dried, and then purified by a silica gel column. A solid intermediate (Ir-021-a) was obtained in 69% yield.
Synthesis of Complex (Ir-021):
Figure BDA0002307000190000253
putting the intermediate (Ir-003-h) (7.6g,1eq) into a single-mouth bottle, adding silver trifluoromethanesulfonate (5.4g,3eq), adding a mixed solution of 300mL of dichloromethane and 100mL of methanol, stirring at 60 ℃, reacting for 6 hours, filtering and drying. Then, the obtained solid was mixed with intermediate (Ir-021-a) (7.58g,1.5eq), a mixed solution of 250mL of ethanol and 250mL of methanol was added, the reaction was stirred at room temperature for 14 hours, and after extraction with dichloromethane, spin-drying, separation and purification were performed by a silica gel column chromatography, followed by recrystallization to obtain a yellow solid complex (Ir-021) in 54% yield.
Synthesis example 5: synthesis complex (Ir-038)
Synthesis of intermediate (Ir-038-a):
Figure BDA0002307000190000254
in a dry two-necked flask was placed 2- (methoxycarbonyl) phenylboronic acid (26.09g,1eq), intermediate (Ir-013-b) (40g,1eq), Pd (PPh)3)4(8.38g,0.05eq) and potassium carbonate (80g,4eq), then 500mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 80 ℃ for 10 hours, the reaction was cooled to room temperature, after completion of the reaction, the reaction was spin-dried, separated by dichloromethane and water, dried over magnesium sulfate and then spin-dried, and then subjected to separation and purification by a silica gel chromatography column. A solid intermediate (Ir-038-a) was obtained in 93% yield.
Synthesis of intermediate (Ir-038-b):
Figure BDA0002307000190000255
the intermediate (Ir-038-a) (40g,1eq) was placed in a dry two-necked flask, 300mL of anhydrous tetrahydrofuran was added as a solvent, methylmagnesium bromide (72g,5eq) was then added, the reaction was stirred at 60 ℃ for 12 hours, cooled to room temperature, and after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and then spin-dried, and then isolated and purified by silica gel chromatography. A solid intermediate (Ir-038-b) was obtained in 79% yield.
Synthesis of intermediate (Ir-038-c):
Figure BDA0002307000190000261
after placing the intermediate (Ir-038-b) (30g,1eq) in a dry two-necked flask, 100mL of hydrochloric acid (HCl) and 100mL of glacial acetic acid were added, and the mixture was stirred at 100 ℃ for 24 hours, cooled to room temperature, spun dry after completion of the reaction, separated with dichloromethane and sodium carbonate solution, dried over magnesium sulfate and then spun dry, and then purified by separation on a silica gel column. A solid intermediate (Ir-038-c) was obtained in 54% yield.
Synthesis of intermediate (Ir-038-d):
Figure BDA0002307000190000262
place pinacol diboron (24.15g,1.5eq), intermediate (Ir-038-c) (19.86g,1eq), Pd (dppf) in a dry, two-necked flask2Cl2(2.3g,0.05eq) and potassium acetate (24g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 100 ℃ for 12 hours, the mixture was cooled to room temperature, after the reaction was completed, the mixture was spin-dried, separated by dichloromethane and water, dried over magnesium sulfate and then spin-dried, and then separated and purified by a silica gel column chromatography. A solid intermediate (Ir-038-d) was obtained in 75% yield.
Synthesis of intermediate (Ir-038-e):
Figure BDA0002307000190000263
in a dry two-necked flask was placed 2-bromopyridine (5.19g,1.2eq), intermediate (Ir-038-d) (9.86g, 1eq), Pd (PPh)3)4(1.58g,0.05eq), potassium carbonate (15.12g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 95 ℃ for 12 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and spin-dried, and then subjected to separation and purification by a silica gel chromatography column. A solid intermediate (Ir-038-e) was obtained in 82% yield.
Synthesis of intermediate (Ir-038-f):
Figure BDA0002307000190000264
putting 7, 8-benzoquinoline (9.36g,3eq) into a single-neck bottle, adding iridium trichloride (5.2g,1eq), adding a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of water, heating to 110 ℃, reacting for 12 hours, cooling to room temperature, pouring into an aqueous solution of sodium chloride, filtering, and drying to obtain an intermediate (Ir-038-f) with a yield of 63%.
Synthesis of Complex (Ir-038):
Figure BDA0002307000190000265
putting the intermediate (Ir-038-f) (10g,1eq) into a single-mouth bottle, adding silver trifluoromethanesulfonate (6.60g,3eq), adding a mixed solution of 300mL of dichloromethane and 100mL of methanol, stirring at 60 ℃, reacting for 6 hours, filtering and drying. Then, the obtained solid was mixed with intermediate (Ir-038-e) (8g,3eq), and a mixed solution of 250mL of ethanol and 250mL of methanol was added, and the mixture was stirred at room temperature for 14 hours, extracted with dichloromethane, spin-dried, then separated and purified by a silica gel column chromatography, and then recrystallized to obtain a yellow solid complex (Ir-038) with a yield of 47%.
Synthetic example 6: synthesis complex (Ir-072)
Synthesis intermediate (Ir-072-a):
Figure BDA0002307000190000271
in a dry two-necked bottle were placed 3-mercaptoindole (25g,1eq), 1, 3-dibromo-2-iodobenzene (60.62g,1eq), cesium carbonate Cs2CO3(109.18g,6eq) and a small amount of copper flakes (3.47g,0.001eq), followed by addition of 250mL of dimethylformamide, reaction at 130 ℃ for 24 hours, removal of the solvent by vacuum distillation, separation with dichloromethane and water, drying over magnesium sulfate and spin-drying of the dichloromethane layer, and separation and purification with a silica gel column. A solid was obtained as intermediate (Ir-072-a) in 83% yield.
Synthesis intermediate (Ir-072-b):
Figure BDA0002307000190000272
after placing the intermediate (Ir-072-a) (20g,1eq), iodobenzene (21.3g, 2eq), sodium tert-butoxide (15.05g, 3eq) and a small amount of cuprous iodide (0.49g,0.05eq) in a dry two-necked flask, 100mL of tetrahydrofuran was added as a solution, and the mixture was stirred at 80 ℃ for 6 hours, cooled to room temperature, spun-dried after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate, spun-dried, and then purified by a silica gel column. The solid intermediate (Ir-072-b) was obtained in 76% yield.
Synthesis intermediate (Ir-072-c):
Figure BDA0002307000190000273
in a dry two-necked flask, intermediate (Ir-072-b) (20g,1eq), cesium 2, 2-dimethylpropionic acid (20.39g, 2eq) and a small amount of PdCl were placed2(PPh3)4(2.67g,0.05eq), then 250mL of dimethylformamide was added as a solution, the reaction was stirred at 80 ℃ for 6 hours, cooled to room temperature, and after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and then spin-dried, and then purified by a silica gel column.The solid intermediate (Ir-072-c) was obtained in 60% yield.
Synthesis intermediate (Ir-072-d):
Figure BDA0002307000190000274
in a dry two-necked flask was placed 2-bromopyridine (5.19g,1.2eq), intermediate (Ir-072-c) (10.36g, 1eq), Pd (PPh)3)4(1.58g,0.05eq), potassium carbonate (15.12g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 95 ℃ for 12 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and spin-dried, and then subjected to separation and purification by a silica gel chromatography column. The solid intermediate (Ir-072-d) was obtained in 91% yield.
Synthesis of Complex (Ir-072):
Figure BDA0002307000190000275
putting the intermediate (Ir-003-h) (7.6g,1eq) into a single-mouth bottle, adding silver trifluoromethanesulfonate (5.4g,3eq), adding a mixed solution of 300mL of dichloromethane and 100mL of methanol, stirring at 60 ℃, reacting for 6 hours, filtering and drying. Then, the obtained solid was mixed with intermediate (Ir-072-d) (8g,3eq), a mixed solution of 250mL of ethanol and 250mL of methanol was added, the mixture was stirred at room temperature for 14 hours, extracted with dichloromethane, spin-dried, then separated and purified by a silica gel column chromatography, and then recrystallized to obtain yellow solid complex (Ir-072) with a yield of 43%.
Synthetic example 7: synthesis complex (Ir-192)
Synthesis intermediate (Ir-192-a):
Figure BDA0002307000190000276
placing 2-amino-5-bromobenzaldehyde (10.05g,1eq), carbon tetrabromide (50g,3eq) and triphenylphosphine (79g,6eq) in a dry double-mouth bottle, adding 500mL dichloromethane as a solution in an ice bath at 0 ℃, reacting for 0.5 hour, adding 44mL triethylamine, reacting for 2 hours at normal temperature, performing spin-drying after the reaction is completed, separating with dichloromethane and water, drying with magnesium sulfate, performing spin-drying, and performing separation and purification by using a silica gel chromatographic column. A solid was obtained as intermediate (Ir-192-a) in 90% yield.
Synthesis intermediate (Ir-192-b):
Figure BDA0002307000190000281
after placing the intermediate (Ir-192-a) (20g,1eq), potassium phosphate (23.85g,2eq), and cuprous iodide (0.54g,0.05eq) in a dry two-necked flask, 500mL of tetrahydrofuran was added as a solution, and the mixture was stirred at 80 ℃ for 8 hours, cooled to room temperature, spun-dried after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate, spun-dried, and then purified by separation with a silica gel column. The solid intermediate (Ir-192-b) was obtained in 88% yield.
Synthesis intermediate (Ir-192-c):
Figure BDA0002307000190000282
in a dry two-necked flask was placed 2-nitrophenylboronic acid (27.8g,0.9eq), intermediate (Ir-192-b) (50.88g, 1eq), Pd (PPh)3)4(10.69g,0.05eq) and potassium carbonate (102g,4eq), then 500mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 80 ℃ for 10 hours, the mixture was cooled to room temperature, after the reaction was completed, the mixture was spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and then spin-dried, and then subjected to separation and purification by a silica gel chromatography column. The solid intermediate (Ir-192-c) was obtained in 72% yield.
Synthesis intermediate (Ir-192-d):
Figure BDA0002307000190000283
place pinacol diboron (24.15g,1.5eq), intermediate (Ir-192-c) (20.10g,1eq), Pd (dppf)2Cl2(2.3g,0.05eq) and potassium acetate (24g,4eq), then adding 250mL of a mixed solution of dioxane and water in a ratio of 3:1, stirring and reacting at 100 ℃ for 12 hours, cooling to room temperature, performing spin-drying after the reaction is completed, separating liquid by dichloromethane and water, drying by magnesium sulfate, then performing spin-drying, and then performing separation and purification by a silica gel chromatographic column. The solid intermediate (Ir-192-d) was obtained in 69% yield.
Synthesis intermediate (Ir-192-e):
Figure BDA0002307000190000284
in a dry two-necked flask was placed 2-bromopyridine (5.19g,1.2eq), intermediate (Ir-192-d) (9.97g, 1eq), Pd (PPh)3)4(1.58g,0.05eq), potassium carbonate (15.12g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 95 ℃ for 12 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and spin-dried, and then subjected to separation and purification by a silica gel chromatography column. The solid intermediate (Ir-192-e) was obtained in 81% yield.
Synthesis intermediate (Ir-192-f):
Figure BDA0002307000190000285
after placing the intermediate (Ir-192-e) (3.80g, 1eq) and triphenylphosphine (15.8g,5eq) in a dry two-necked flask, 150mL of 1, 2-dichlorobenzene was added as a solution, and the mixture was stirred at 160 ℃ for 12 hours, cooled to room temperature, dried after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate, and then dried, and then separated and purified by a silica gel column chromatography. The solid intermediate (Ir-192-f) was obtained in 93% yield.
Synthesis intermediate (Ir-192-g):
Figure BDA0002307000190000286
after placing the intermediate (Ir-192-f) (5g,1eq), sodium hydride (1.69g,4eq) and methyl iodide (10.02g,4eq) in a dry two-necked flask, 50mL of tetrahydrofuran was added as a solution, and the mixture was stirred at 80 ℃ for 6 hours, cooled to room temperature, spun dry after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate and then spun dry, and then separated and purified by a silica gel column chromatography. A solid intermediate (Ir-192-g) was obtained in 95% yield.
Synthesis of Complex (Ir-192):
Figure BDA0002307000190000291
putting the intermediate (Ir-003-h) (7.6g,1eq) into a single-mouth bottle, adding silver trifluoromethanesulfonate (5.4g,3eq), adding a mixed solution of 300mL of dichloromethane and 100mL of methanol, stirring at 60 ℃, reacting for 6 hours, filtering and drying. Then, the obtained solid was mixed with intermediate (Ir-192-g) (6.62g,3eq), a mixed solution of 250mL of ethanol and 250mL of methanol was added, the reaction was stirred at room temperature for 14 hours, and the mixture was extracted with dichloromethane, spin-dried, separated and purified by a silica gel column chromatography, and then recrystallized to obtain a yellow solid complex (Ir-192) with a yield of 39%.
Synthesis example 8: synthesis of Complex (Pt-207)
Synthesis of intermediate (Pt-207-a):
Figure BDA0002307000190000292
in a dry two-necked flask was placed 2-bromoquinoline (6.83g,1.2eq), intermediate (Ir-003-d) (10g,1eq), Pd (PPh)3)4(1.58g,0.05eq), potassium carbonate (15.12g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 95 ℃ for 12 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and spin-dried, and then subjected to separation and purification by a silica gel chromatography column. A solid intermediate (Pt-207-a) was obtained in 74% yield.
Synthesis of intermediate (Pt-207-b):
Figure BDA0002307000190000293
after placing the intermediate (Pt-207-a) (4.41g, 1eq) and triphenylphosphine (15.8g,5eq) in a dry two-necked flask, 150mL of 1, 2-dichlorobenzene was added as a solution, and the mixture was stirred at 160 ℃ for 12 hours, cooled to room temperature, dried after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate, and then dried, and then isolated and purified by a silica gel column chromatography. A solid intermediate (Pt-207-b) was obtained in 58% yield.
Synthesis of intermediate (Pt-207-c):
Figure BDA0002307000190000294
after placing the intermediate (Pt-207-b) (5g,1eq), sodium hydride (0.71g,2eq), and methyl iodide (4.24g,2eq) in a dry two-necked flask, 50mL of tetrahydrofuran was added as a solution, and the mixture was stirred at 80 ℃ for 6 hours, cooled to room temperature, spun dry after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate, spun dry, and then purified by separation with a silica gel column. A solid intermediate (Pt-207-c) was obtained in 98% yield.
Synthesis of intermediate (Pt-207-d):
Figure BDA0002307000190000295
putting 1-phenylisoquinoline (7.71g,3eq) into a single-mouth bottle, adding potassium chloroplatinite (5.2g,1eq), adding a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of water, heating to 110 ℃, reacting for 12 hours, cooling to room temperature, pouring into an aqueous solution of sodium chloride, filtering, and drying to obtain an intermediate (Pt-207-d) with the yield of 70%.
Synthesis of Complex (Pt-207):
Figure BDA0002307000190000301
putting the intermediate (Pt-207-d) (7.6g,1eq) into a single-mouth bottle, adding silver trifluoromethanesulfonate (6.74g,3eq), adding a mixed solution of 300mL of dichloromethane and 100mL of methanol, stirring at 60 ℃, reacting for 6 hours, filtering and drying. Then, the obtained solid was mixed with intermediate (Pt-207-c) (9.14g,3eq), a mixed solution of 250mL of ethanol and 250mL of methanol was added, the reaction was stirred at room temperature for 14 hours, and the mixture was extracted with methylene chloride, spin-dried, separated and purified by a silica gel column, and then recrystallized to obtain red solid complex (Pt-207) with a yield of 39%.
Synthetic example 9: synthesis complex (Ir-208)
Synthesis intermediate (Ir-208-a):
Figure BDA0002307000190000302
putting the intermediate (Pt-207-c) (17.5g,3eq) into a single-mouth bottle, adding iridium trichloride (5g,1eq), adding a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of water, heating to 110 ℃, reacting for 12 hours, cooling to room temperature, pouring into an aqueous solution of sodium chloride, filtering, and drying to obtain an intermediate (Ir-208-a) with the yield of 65%.
Synthesis of Complex (Ir-208):
Figure BDA0002307000190000303
putting the intermediate (Ir-208-a) (7.6g,1eq) into a single-mouth bottle, adding silver trifluoromethanesulfonate (3.18g,3eq), adding a mixed solution of 300mL of dichloromethane and 100mL of methanol, stirring at 60 ℃, reacting for 6 hours, filtering and drying. Then, the obtained solid was mixed with acetylacetone (1.24g,3eq), a mixed solution of 250mL of ethanol and 250mL of methanol was added, the mixture was stirred at room temperature for 14 hours, and the mixture was extracted with dichloromethane, spin-dried, and then subjected to separation and purification with a silica gel column, followed by recrystallization to obtain a red solid complex (Ir-208) with a yield of 49%.
Synthetic example 10: synthesis of Complex (Pt-218)
Synthesis intermediate (Pt-218-a):
Figure BDA0002307000190000304
in a trunkIn a dry two-necked flask, 2-bromoquinoline (6.83g,1.2eq), intermediate (Ir-013-d) (10g,1eq), Pd (PPh)3)4(1.58g,0.05eq), potassium carbonate (15.12g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 95 ℃ for 12 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and spin-dried, and then subjected to separation and purification by a silica gel chromatography column. A solid intermediate (Pt-218-a) was obtained in 61% yield.
Synthesis of intermediate (Pt-218-b):
Figure BDA0002307000190000305
after placing the intermediate (Pt-218-a) (4.41g, 1eq) and triphenylphosphine (15.8g,5eq) in a dry two-necked flask, 150mL of 1, 2-dichlorobenzene was added as a solution, and the mixture was stirred at 160 ℃ for 12 hours, cooled to room temperature, dried after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate, and then dried, and then isolated and purified by a silica gel column chromatography. A solid intermediate (Pt-218-b) was obtained in 52% yield.
Synthesis of intermediate (Pt-218-c):
Figure BDA0002307000190000311
after placing the intermediate (Pt-218-b) (5g,1eq), sodium hydride (0.71g,2eq), and methyl iodide (4.24g,2eq) in a dry two-necked flask, 50mL of tetrahydrofuran was added as a solution, and the mixture was stirred at 80 ℃ for 6 hours, cooled to room temperature, spun dry after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate, spun dry, and then purified by separation with a silica gel column. The solid intermediate (Pt-218-c) was obtained in 90% yield.
Synthesis of intermediate (Pt-218-d):
Figure BDA0002307000190000312
1-phenylpyridine (5.83g,3eq) was placed in a single vial, potassium chloroplatinite (5.2g,1eq) was added, a mixed solution of 300mL ethylene glycol ethyl ether and 100mL water was added, the mixture was heated to 110 ℃, reacted for 12 hours, cooled to room temperature, poured into an aqueous sodium chloride solution, filtered, and dried to obtain an intermediate (Pt-218-d) in 66% yield.
Synthesis of Complex (Pt-218):
Figure BDA0002307000190000313
the intermediate (Pt-218-d) (7.6g,1eq) was placed in a single vial, silver trifluoromethanesulfonate (7.61g,3eq) was added, a mixed solution of 300mL of methylene chloride and 100mL of methanol was added, and the mixture was stirred at 60 ℃ for reaction for 6 hours, filtered and dried. Then, the obtained solid was mixed with intermediate (Pt-218-c) (10.32g,3eq), a mixed solution of 250mL of ethanol and 250mL of methanol was added, the reaction was stirred at room temperature for 14 hours, and the mixture was extracted with methylene chloride, spin-dried, separated and purified by a silica gel column, and then recrystallized to obtain red solid complex (Pt-218) with a yield of 34%.
Synthetic example 11: synthesis complex (Ir-223)
Synthesis intermediate (Ir-223-a):
Figure BDA0002307000190000314
in a dry two-necked flask, 1-bromoisoquinoline (6.83g,1.2eq), intermediate (Ir-003-d) (10g,1eq), Pd (PPh) were placed3)4(1.58g,0.05eq), potassium carbonate (15.12g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 95 ℃ for 12 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and spin-dried, and then subjected to separation and purification by a silica gel chromatography column. The solid intermediate (Ir-223-a) was obtained in 79% yield.
Synthesis intermediate (Ir-223-b):
Figure BDA0002307000190000315
after placing the intermediate (Ir-223-a) (4.41g, 1eq) and triphenylphosphine (15.8g,5eq) in a dry two-necked flask, 150mL of 1, 2-dichlorobenzene was added as a solution, and the mixture was stirred at 160 ℃ for 12 hours, cooled to room temperature, dried after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate, and then dried, and then separated and purified by a silica gel column chromatography. A solid intermediate (Ir-223-b) was obtained in 74% yield.
Synthesis intermediate (Ir-223-c):
Figure BDA0002307000190000316
after placing the intermediate (Ir-223-b) (5g,1eq), sodium hydride (0.71g,2eq) and methyl iodide (4.24g,2eq) in a dry two-necked flask, 50mL of tetrahydrofuran was added as a solution, and the mixture was stirred at 80 ℃ for 6 hours, cooled to room temperature, spun dry after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate and then spun dry, and then separated and purified by a silica gel column chromatography. The solid intermediate (Ir-223-c) was obtained in 67% yield.
Synthesis intermediate (Ir-223-d):
Figure BDA0002307000190000321
putting the intermediate (Ir-223-c) (17.5g,3eq) into a single-mouth bottle, adding iridium trichloride (5g,1eq), adding a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of water, heating to 110 ℃, reacting for 12 hours, cooling to room temperature, pouring into an aqueous solution of sodium chloride, filtering, and drying to obtain the intermediate (Ir-223-d) with the yield of 58%.
Synthesis of Complex (Ir-223):
Figure BDA0002307000190000322
putting the intermediate (Ir-223-d) (7.6g,1eq) into a single-mouth bottle, adding silver trifluoromethanesulfonate (3.18g,3eq), adding a mixed solution of 300mL of dichloromethane and 100mL of methanol, stirring at 60 ℃, reacting for 6 hours, filtering and drying. Then, the obtained solid was mixed with acetylacetone (1.24g,3eq), a mixed solution of 250mL of ethanol and 250mL of methanol was added, the mixture was stirred at room temperature for 14 hours, and the mixture was extracted with dichloromethane, spin-dried, and then subjected to separation and purification with a silica gel column, followed by recrystallization to obtain a red solid complex (Ir-223) with a yield of 66%.
Synthetic example 12: synthesis complex (Ir-239)
Synthesis intermediate (Ir-239-a):
Figure BDA0002307000190000323
in a dry two-necked flask was placed pinacol diboron (24.15g,1.5eq), 1-bromobenzoic acid (19.47g,1eq), Pd (dppf)2Cl2(2.3g,0.05eq) and potassium acetate (24g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 100 ℃ for 12 hours, the mixture was cooled to room temperature, after the reaction was completed, the mixture was spin-dried, separated by dichloromethane and water, dried over magnesium sulfate and then spin-dried, and then separated and purified by a silica gel column chromatography. The solid intermediate (Ir-239-a) was obtained in 87% yield.
Synthesis intermediate (Ir-239-b):
Figure BDA0002307000190000324
in a dry two-necked flask was placed 2-bromopyridine (5.19g,1.2eq), intermediate (Ir-239-a) (9.70g, 1eq), Pd (PPh)3)4(1.58g,0.05eq), potassium carbonate (15.11g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 95 ℃ for 12 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and spin-dried, and then subjected to separation and purification by a silica gel chromatography column. The solid intermediate (Ir-239-b) was obtained in 56% yield.
Synthesis intermediate (Ir-239-c):
Figure BDA0002307000190000325
putting 2- (2-pyridine) -benzimidazole (16.26g,5eq) and potassium carbonate (11.55g,5eq) into a single-neck bottle, adding iridium trichloride (5g,1eq), adding a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of water, heating to 110 ℃, reacting for 12 hours, cooling to room temperature, pouring into an aqueous solution of sodium chloride, filtering, and drying to obtain an intermediate (Ir-239-c) with the yield of 44%.
Synthesis of complex (Ir-239):
Figure BDA0002307000190000331
putting the intermediate (Ir-239-c) (7.6g,1eq) into a single-mouth bottle, adding silver trifluoromethanesulfonate (4.79g,3eq), adding a mixed solution of 300mL of dichloromethane and 100mL of methanol, stirring at 60 ℃, reacting for 6 hours, filtering and drying. Then, the obtained solid was mixed with intermediate (Ir-239-b) (5.69g,3eq), a mixed solution of 250mL of ethanol and 250mL of methanol was added, the reaction was stirred at room temperature for 14 hours, and the mixture was extracted with dichloromethane, dried by spinning, separated and purified by a silica gel column chromatography, and then recrystallized to obtain a yellow solid complex (Ir-239) with a yield of 35%.
Synthetic example 13: synthesis complex (Ir-240)
Synthesis intermediate (Ir-240-a):
Figure BDA0002307000190000332
in a dry two-necked flask was placed pinacol diboron (24.15g,1.5eq), 2, 6-dibromophenol (15.9g,1eq), Pd (dppf)2Cl2(2.3g,0.05eq) and potassium acetate (24g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 100 ℃ for 12 hours, the mixture was cooled to room temperature, after the reaction was completed, the mixture was spin-dried, separated by dichloromethane and water, dried over magnesium sulfate and then spin-dried, and then separated and purified by a silica gel column chromatography. A solid intermediate (Ir-240-a) was obtained in 69% yield.
Synthesis intermediate (Ir-240-b):
Figure BDA0002307000190000333
in a dry two-necked flask, 1-iodo-2-bromonaphthalene (5.19g,1.2eq), intermediate (Ir-240-a) (3.88g, 1eq), Pd (PPh) were placed3)4(0.75g,0.05eq), potassium carbonate (7.17g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 95 ℃ for 12 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and spin-dried, and then subjected to separation and purification by a silica gel chromatography column. A solid intermediate (Ir-240-b) was obtained in 48% yield.
Synthesis intermediate (Ir-240-c):
Figure BDA0002307000190000334
after placing the intermediate (Ir-240-b) (20g,1eq), potassium phosphate (22.46g,2eq), and cuprous iodide (0.5g,0.05eq) in a dry two-necked flask, 500mL of tetrahydrofuran was added as a solution, and the mixture was stirred at 80 ℃ for 8 hours, cooled to room temperature, spun-dried after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate, spun-dried, and then purified by separation with a silica gel column. The solid intermediate (Ir-240-c) was obtained in 67% yield.
Synthesis intermediate (Ir-240-d):
Figure BDA0002307000190000335
place pinacol diboron (24.15g,1.5eq), intermediate (Ir-240-c) (18.83g,1eq), Pd (dppf) in a dry, two-necked flask2Cl2(2.3g,0.05eq) and potassium acetate (24g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 100 ℃ for 12 hours, the mixture was cooled to room temperature, after the reaction was completed, the mixture was spin-dried, separated by dichloromethane and water, dried over magnesium sulfate and then spin-dried, and then separated and purified by a silica gel column chromatography. A solid intermediate (Ir-240-d) was obtained in 69% yield.
Synthesis intermediate (Ir-240-e):
Figure BDA0002307000190000341
in a dry two-necked flask, 1-bromoisoquinoline (6.83g,1.2eq), intermediate (Ir-240-d) (9.42g, 1eq), Pd (PPh) were placed3)4(1.58g,0.05eq), potassium carbonate (15.12g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 95 ℃ for 12 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and spin-dried, and then subjected to separation and purification by a silica gel chromatography column. The solid intermediate (Ir-240-e) was obtained in 58% yield.
Synthesis of Complex (Ir-240):
Figure BDA0002307000190000342
putting the intermediate (Ir-038-f) (10g,1eq) into a single-mouth bottle, adding silver trifluoromethanesulfonate (6.60g,3eq), adding a mixed solution of 300mL of dichloromethane and 100mL of methanol, stirring at 60 ℃, reacting for 6 hours, filtering and drying. Then, the obtained solid was mixed with intermediate (Ir-240-e) (8.87g,3eq), a mixed solution of 250mL of ethanol and 250mL of methanol was added, the reaction was stirred at room temperature for 14 hours, and the mixture was extracted with dichloromethane, spin-dried, separated and purified by a silica gel column chromatography, and then recrystallized to obtain a red solid complex (Ir-240) with a yield of 45%.
Synthesis example 14: synthesis of complex (Ir-243)
Synthesis intermediate (Ir-243-a):
Figure BDA0002307000190000343
in a dry two-necked flask were placed pinacol diboron (24.15g,1.5eq), 1,2, 7-tribromonaphthalene (23.13g,1eq), Pd (dppf)2Cl2(2.3g,0.05eq), potassium acetate (24g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 100 ℃ for 12 hours, cooled to room temperature, and reactedAfter completion, the extract was spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and then spin-dried, and then separated and purified by a silica gel column chromatography. A solid intermediate (Ir-243-a) was obtained in 69% yield.
Synthesis intermediate (Ir-243-b):
Figure BDA0002307000190000344
in a dry two-necked flask, 2-iodoanisole (7.26g,1.2eq), intermediate (Ir-243-a) (10g,1eq), Pd (PPh) were placed3)4(1.40g,0.05eq), potassium carbonate (13.42g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 95 ℃ for 12 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and spin-dried, and then subjected to separation and purification by a silica gel chromatography column. A solid intermediate (Ir-243-b) was obtained in 67% yield.
Synthesis intermediate (Ir-243-c):
Figure BDA0002307000190000345
the intermediate (Ir-243-b) (10g,1eq), potassium phosphate (10.4g,2eq), and cuprous iodide (0.23g,0.05eq) were placed in a dry double-neck flask, and then 500mL of tetrahydrofuran was added as a solution, stirred at 80 ℃ for reaction for 8 hours, cooled to room temperature, spun-dried after completion of the reaction, separated with dichloromethane and water, dried over magnesium sulfate, and then spun-dried, followed by separation and purification with a silica gel column. A solid intermediate (Ir-43-c) was obtained in 35% yield.
Synthesis intermediate (Ir-243-d):
Figure BDA0002307000190000346
place pinacol diboron (24.15g,1.5eq), intermediate (Ir-243-c) (19.86g,1eq), Pd (dppf)2Cl2(2.3g,0.05eq), potassium acetate (24g,4eq), then 250mL of dioxahexa-zine at a 3:1 ratioAnd (3) stirring the mixed solution of the ring and water at 100 ℃ for reaction for 12 hours, cooling to room temperature, performing spin-drying after the reaction is finished, separating liquid by using dichloromethane and water, drying by using magnesium sulfate, performing spin-drying, and performing separation and purification by using a silica gel chromatographic column. A solid intermediate (Ir-243-d) was obtained in 39% yield.
Synthesis intermediate (Ir-243-e):
Figure BDA0002307000190000351
in a dry two-necked flask, 1-bromoisoquinoline (6.83g,1.2eq), intermediate (Ir-243-d) (9.86g, 1eq), Pd (PPh) were placed3)4(1.58g,0.05eq), potassium carbonate (15.12g,4eq), then 250mL of a mixed solution of dioxane and water in a ratio of 3:1 was added, the reaction was stirred at 95 ℃ for 12 hours, cooled to room temperature, after completion of the reaction, spin-dried, separated with dichloromethane and water, dried over magnesium sulfate and spin-dried, and then subjected to separation and purification by a silica gel chromatography column. A solid intermediate (Ir-243-e) was obtained in 64% yield.
Synthesis of Complex (Ir-243):
Figure BDA0002307000190000352
putting the intermediate (Ir-243-e) (12.11g,5eq), iridium trichloride (2.00g,1eq) and potassium carbonate (4.62g,5eq) into a single-mouth bottle, adding 250mL of glycerol as a solvent, and heating to 300 ℃ for reaction for 24 hours. After completion of the reaction, it was cooled to room temperature, and 2000mL of water was added to precipitate a yellow solid, which was filtered and washed with water and methanol to obtain a yellow solid complex (Ir-243) in 77% yield after recrystallization.
Preparation and characterization of OLED devices
The structure of the OLED device is as follows:
Figure BDA0002307000190000355
wherein the EML is formed by H-Host and E-Host with the ratio of 6:4 and is doped with 10% w/w of (Ir-003), or (Ir-013), or (Ir-018), or (Ir-021), or (Ir-038), or (Ir-07)2) Or (Ir-192) or (Ir-208) or (Ir-223) or (Ir-239) or (Ir-240) or (Ir-243) or Ir (ppy)3Or Ir (pq)2(acac). The ETL consisted of LiQ (8-hydroxyquinoline-lithium) doped with 40% w/w ETM. The material structure used for the device is as follows:
Figure BDA0002307000190000353
the preparation steps of the OLED device are as follows:
a. cleaning the conductive glass substrate: for the first time, the cleaning agent can be cleaned by various solvents, such as chloroform, ketone and isopropanol, and then ultraviolet ozone plasma treatment is carried out;
b、
Figure BDA0002307000190000356
under high vacuum (1X 10)-6Mbar, mbar) by thermal evaporation;
c. cathode: LiF/Al (1nm/150nm) in high vacuum (1X 10)-6Millibar) hot evaporation;
d. packaging: the devices were encapsulated with uv curable resin in a nitrogen glove box.
The current-voltage-luminance (JVL) characteristics of OLED devices are characterized by characterization equipment, while recording important parameters such as maximum emission wavelength, external quantum efficiency. Detected with a classical phosphorescent green dopant Ir (ppy)3Relative comparison, relative external quantum efficiency parameter and relative lifetime T of OLED device95@50mA·cm–2As shown in table two:
green light complex data (Table II)
Figure BDA0002307000190000354
Figure BDA0002307000190000361
Detected with the classic phosphorescent red dopant Ir (acac) (pq)2Relative comparison, relative exterior of OLED deviceQuantum efficiency parameter and relative lifetime T95@50mA·cm–2As shown in table three:
red light complex data (third table)
Figure BDA0002307000190000362
It can be seen from the devices made from different red and green Ir (III) complexes, that if the phenyl group of 2-phenylpyridine is modified by the five-membered ring group with a specific structure, higher luminous efficiency and device lifetime can be effectively provided. The reason is estimated to be that the ligand can prolong the whole length of the complex, so that the light-emitting plane in a specific direction is increased, thereby improving the light-emitting efficiency and having good stability. And different atoms can be matched, so that different light colors can be adjusted, and more saturated light colors can be obtained. Therefore, the metal complex containing the group can also improve the brightness and current efficiency of the device, and simultaneously reduce the starting voltage, thereby further improving the service life of the device.
The organic transition metal complex is used in OLED, especially as the doping material of the luminous layer, and can provide higher luminous efficiency and device life.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification 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 the application of the present invention is not limited to the above examples, and that several variations and modifications can be made by those skilled in the art without departing from the spirit of the present invention, which falls into the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (13)

1. An organic transition metal complex characterized by having a general structural formula shown in chemical formula (1):
Figure FDA0002307000180000011
wherein:
m is a metal atom which is iridium, gold, platinum, ruthenium, rhodium, osmium, rhenium, nickel, copper, silver, zinc, tungsten or palladium;
each L is independently an ancillary ligand;
n is selected from 1,2 or 3; m is selected from 0 or 1 or 2;
each Ar1Independently from each other: r1Substituted or unsubstituted aromatic radical having 5 to 20 ring atoms, R1Substituted or unsubstituted heteroaromatic radical having 5 to 20 ring atoms or R1A substituted or unsubstituted non-aromatic ring system having 5 to 20 ring atoms;
Ar2、Ar3、Ar4independently selected from R1Substituted or unsubstituted aromatic radical having 5 to 6 ring atoms, R1Substituted or unsubstituted heteroaromatic radical having 5 to 6 ring atoms or R1A substituted or unsubstituted non-aromatic ring system having 5 to 6 ring atoms;
x is selected from CR1Or N;
R1selected from the group consisting of hydrogen, deuterium, halogen, linear alkanes having 1 to 30 carbon atoms, branched alkanes having 1 to 30 carbon atoms, linear alkenes having 1 to 30 carbon atoms, branched alkenes having 1 to 30 carbon atoms, alkane ethers having 1 to 30 carbon atoms, aromatic groups having 1 to 30 carbon atoms, heteroaromatic groups having 1 to 30 carbon atoms or non-aromatic ring systems having 1 to 30 carbon atoms.
2. The organic transition metal complex according to claim 1, characterized in that: the chemical formula (1) is selected from the chemical formula (2-1) or the chemical formula (2-2):
Figure FDA0002307000180000012
3. the organic transition metal complex according to claim 2, characterized in that:
Figure FDA0002307000180000013
selected from any one of the structures (A-1) and (A-4):
Figure FDA0002307000180000014
wherein:
y is selected from CR2R3、NR2、O、S、SiR2R3Or Se;
v is selected from CR4Or N or C; at least two adjacent V are selected from C and are linking sites;
R2to R4Selected from the group consisting of hydrogen, deuterium, halogen, linear alkanes having 1 to 30 carbon atoms, branched alkanes having 1 to 30 carbon atoms, linear alkenes having 1 to 30 carbon atoms, branched alkenes having 1 to 30 carbon atoms, alkane ethers having 1 to 30 carbon atoms, aromatic groups having 1 to 30 carbon atoms, heteroaromatic groups having 1 to 30 carbon atoms or non-aromatic ring systems having 1 to 30 carbon atoms;
denotes the attachment site.
4. An organic transition metal complex according to claim 3, characterized in that:
Figure FDA0002307000180000015
is selected from (A-1) or (A-2).
5. The organic transition metal complex according to claim 1, characterized in that: ar (Ar)1Selected from the group consisting of:
Figure FDA0002307000180000021
wherein:
Y1selected from the group consisting of CR5R6、NR5、O、S、SiR5R6Or Se;
X1selected from the group consisting of CR5Or N or C; at least two adjacent V are selected from C and are linking sites;
R5-R6selected from the group consisting of hydrogen, deuterium, halogen, linear alkanes having 1 to 30 carbon atoms, branched alkanes having 1 to 30 carbon atoms, linear alkenes having 1 to 30 carbon atoms, branched alkenes having 1 to 30 carbon atoms, alkane ethers having 1 to 30 carbon atoms, aromatic groups having 1 to 30 carbon atoms, heteroaromatic groups having 1 to 30 carbon atoms or non-aromatic ring systems having 1 to 30 carbon atoms.
6. The organic transition metal complex according to claim 5, characterized in that: ar (Ar)1Selected from the group consisting of:
Figure FDA0002307000180000022
wherein: # denotes linkage to Ar2The attachment site of (a); m has the meaning of claim 1.
7. The organic transition metal complex according to any one of claims 1 to 6, wherein the formula (1) is selected from any general formula of (B-1) to (B-36):
Figure FDA0002307000180000023
Figure FDA0002307000180000031
8. an organic transition metal complex according to claim 1, characterized in that L is a monoanionic bidentate chelating ligand, L is selected from the following structures:
Figure FDA0002307000180000041
wherein:
Y1selected from the group consisting of CR5R6、NR5、O、S、SiR5R6Or Se;
X1selected from the group consisting of CR5Or N or C;
R5-R6selected from the group consisting of hydrogen, deuterium, halogen, linear alkanes having 1 to 30 carbon atoms, branched alkanes having 1 to 30 carbon atoms, linear alkenes having 1 to 30 carbon atoms, branched alkenes having 1 to 30 carbon atoms, alkane ethers having 1 to 30 carbon atoms, aromatic groups having 1 to 30 carbon atoms, heteroaromatic groups having 1 to 30 carbon atoms or non-aromatic ring systems having 1 to 30 carbon atoms;
m has the meaning of claim 1.
9. The organic transition metal complex according to claim 8, wherein the formula (1) is selected from (3-1) or (3-2):
Figure FDA0002307000180000042
10. a polymer comprising at least one repeating unit comprising an organic transition metal complex according to any one of claims 1 to 9.
11. A mixture comprising the organic transition metal complex according to any one of claims 1 to 9 or the polymer according to claim 10, and at least one organic functional material 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 material, a host material, and a dopant material.
12. A composition comprising an organic transition metal complex according to any one of claims 1 to 9 or a polymer according to claim 10 or a mixture according to claim 11 and at least one organic solvent.
13. An organic electronic device comprising an organic transition metal complex according to any one of claims 1 to 9 or a polymer according to claim 10 or a mixture according to claim 11 or prepared from a composition according to claim 12.
CN201911243934.7A 2018-12-17 2019-12-06 Organic transition metal complex, polymer, mixture, composition and organic electronic device Pending CN111039987A (en)

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CN114213467A (en) * 2021-12-03 2022-03-22 北京大学深圳研究生院 Phosphorescent light-emitting material based on iridium complex and organic electroluminescent device
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Cited By (5)

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CN114621237A (en) * 2020-12-14 2022-06-14 广州华睿光电材料有限公司 Organic compound, mixture, composition and organic electronic device
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CN112979715A (en) * 2021-03-01 2021-06-18 北京八亿时空液晶科技股份有限公司 Metal complex, organic electroluminescent material, organic electroluminescent element, and electroluminescent device
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