CN116496322A - An organometallic complex containing free radical units, mixtures and compositions comprising the same, and applications thereof in electronic devices - Google Patents

Abstract

The invention discloses an organometallic complex containing a free radical unit and application thereof in organic electronic devices, in particular to organic phosphorescence light emitting diodes. The invention also relates to organic electronic devices, in particular organic light-emitting diodes, comprising organometallic complexes according to the invention containing organic free radical units, and to the use thereof in display and lighting technology. Through device structure optimization, the concentration of the metal complex in the matrix is changed, so that the optimal device performance can be achieved, an OLED device with high efficiency, high brightness and high stability can be conveniently realized, and better material options are provided for full-color display and illumination application.

Description

An organic metal complex containing a free radical unit, a mixture and a composition thereof, and its application in electronic devices

Technical Field

The present invention relates to an organic metal complex containing a free radical unit, a mixture and a composition thereof, and an application thereof in an organic electronic device, in particular an organic spintronic device and an organic light emitting diode. The present invention also relates to an organic electronic device, in particular an organic spintronic device, a light emitting element and an application thereof in a display and a lighting device, comprising such an organic metal complex containing a free radical unit.

Background Art

Organic light-emitting diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat-panel displays and lighting due to the synthetic versatility, relatively low manufacturing cost, and excellent optical and electrical properties of organic semiconductor materials.

In order to improve the luminous efficiency of organic light-emitting diodes, various fluorescent and phosphorescent luminescent material systems have been developed. Organic light-emitting diodes using fluorescent materials have the characteristics of high reliability, but their internal electroluminescent quantum efficiency is limited to 25% under electric field excitation. This is because the probability ratio of excitons to singlet excited states and triplet excited states is 1:3. In 1999, Professor Thomson of the University of Southern California and Professor Forrest of Princeton University doped tri(2-phenylpyridine) iridium Ir(ppy)3 into N,N-dicarbazole biphenyl (CBP) and successfully prepared green electrophosphorescent devices, which aroused people's strong interest in complex phosphorescent materials. Due to the introduction of heavy metals, the molecular spin-orbit coupling is improved, the lifetime of the triplet excited state is shortened, and the intersystem crossing of molecules is enhanced, so that phosphorescence can be smoothly emitted. Moreover, this type of complex has a mild reaction, and the structure and substitution groups of the complex can be easily changed to adjust the emission wavelength, so as to obtain electrophosphorescent materials with excellent performance. So far, the internal quantum efficiency of phosphorescent OLEDs has been close to 100%. However, the emission spectrum of most phosphorescent materials is too wide and the color purity is poor, which is not conducive to high-end display, and the stability of this type of phosphorescent OLED needs to be further improved.

Stable organic free radical compounds based on hydrocarbons have long been discovered and have begun to be used in organic electronic devices, such as organic free radical batteries, see Morita et al., Nature Materials 10, 947 (2011); and in OLEDs, see Feng Li et al., Angew. Chem. Int. Ed. 2015, 54, 1-6. However, the performance of all these organic electronic devices based on organic free radical compounds is still far from being practical.

In addition, organic spin electronics is the basis of the next generation of computing and storage technologies and is a hot topic in research today. Free radical compounds are potential key materials for organic spin electronics devices. High-performance free radical compounds for this purpose are urgently needed to be developed.

Summary of the invention

In view of the demand for free radical materials in the above-mentioned various technical fields, a main purpose of the present invention is to provide an organic metal complex containing free radicals, polymers, mixtures and compositions containing the same, and applications in organic electronic devices; the purpose is to provide a new type of metal complex material containing free radicals. In the prior art, phosphorescent metal complex materials are all neutral complexes. The present invention provides a metal complex material containing different numbers of free radicals, which is convenient for adjusting the energy state structure and spin state of the metal complex, providing more options for material design, improving device performance and providing new material options for the development of new devices. Another object of the present invention is to provide an organic electronic device containing the organic metal complex of the present invention, and applications thereof.

The technical solution of the present invention is as follows:

An organic metal complex has the general formula M(L)n, wherein M is a metal atom, L is an organic ligand, L may be the same or different each time it appears, and is bonded or coordinated to the metal atom M through one or more positions, n is an integer from 1 to 6, characterized in that at least one L contains an organic free radical group.

A polymer comprises at least one repeating unit, wherein the repeating unit comprises a structural unit represented by the general formula M(L)n.

A mixture comprising at least one of the organometallic complexes or polymers described above, and at least another organic functional material, wherein the 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 light-emitting material (Emitter), a host material (Host) and an organic dye.

A composition comprises the above-mentioned organometallic complex or polymer or mixture, and at least one organic solvent.

An organic electronic device comprises the above-mentioned organic metal complex or polymer or mixture.

An organic electronic device as described above, wherein the organic electronic device is selected from an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, an organic spin electronic device, an organic spin valve, a photodiode, an organic sensor and an organic plasma emitting diode (Organic Plasmon Emitting Diode).

Beneficial effects: The present invention introduces free radical units into the organic metal complex to form new compound species with the metal complex, thereby providing more options for the design of phosphorescent materials; the electrical conductivity of the metal complex material is enhanced by introducing new free radical units into the organic metal complex of the present invention, and at the same time, due to the introduction of the free radical units, the spin coupling characteristics of the material are changed, the luminescence efficiency of the phosphorescent metal complex is improved, and more material options are provided for high-efficiency phosphorescent light-emitting devices.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1: EPR spectrum of iridium complex free radical Ir3

DETAILED DESCRIPTION

The present invention provides an organic metal complex and its application in an organic electroluminescent device. To make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

In the present invention, main material, matrix material and Host material have the same meaning and can be interchangeable.

In the embodiments of the present invention, singlet state and singlet state have the same meaning and can be interchangeable.

In the embodiments of the present invention, triplet state and triplet state have the same meaning and can be interchangeable.

In the present invention, "substituted" means that a hydrogen atom in a substituted group is replaced by a substituent.

In the present invention, the "number of ring atoms" refers to the number of atoms in the atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring atoms. The same is true for the "number of ring atoms" described below unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thienyl group is 5.

In the present invention, "adjacent groups" means that these groups are bonded to the same carbon atom or to adjacent carbon atoms. These definitions apply to "adjacent substituents" accordingly.

In the embodiment of the present invention, the energy level structure of the organic material, singlet energy level E _S1 , doublet energy level E _D1 , triplet energy level E _T1 , highest occupied molecular orbital energy level HOMO, lowest unoccupied molecular orbital energy level LUMO play a key role. The determination of these energy levels is introduced below.

HOMO and LUMO energy levels can be measured by photoelectric effects, such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereafter referred to as DFT), have also become effective methods for calculating molecular orbital energy levels.

The singlet energy level E _S1 of the organic material can be determined by luminescence spectroscopy, and the triplet energy level E _T1 can be measured by low-temperature time-resolved luminescence spectroscopy. E _S1, E _D1 and E _T1 can also be obtained by quantum simulation calculation (such as by Time-dependent DFT), such as by commercial software Gaussian 09W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110. ΔE _ST is defined as (E _S1 -E _T1 ).

It should be noted that the absolute values of HOMO, LUMO, _ES1 , _ED1 , and _ET1 depend on the measurement method or calculation method used, and even for the same method, different evaluation methods, such as the starting point and the peak point on the CV curve, may give different HOMO/LUMO values. Therefore, a reasonable and meaningful comparison should be made using the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, the values of HOMO, LUMO, _ES1 , _ED1 , and _ET1 are based on the simulation of Time-dependent DFT, but do not affect the application of other measurement or calculation methods.

The present invention provides an organic metal complex having the general formula M(L)n, wherein M is a metal atom, L is an organic ligand, L can be the same or different each time it appears, and is bonded or coordinated to the metal atom M through one or more positions, n is 1, 2, 3, 4, 5 or 6, and at least one L contains an organic free radical group.

Preferably, the organometallic complex contains a chelating ligand, i.e., it coordinates to the metal via at least two binding points, and it is particularly preferred that the organometallic complex contains two or three identical or different bidentate or multidentate ligands. Chelating ligands are beneficial to improving the stability of the metal complex.

In a preferred embodiment, the organometallic complex has the following form:

Wherein: Ar ₁ and Ar ₂ may be the same or different each time they appear, and are a cyclic group; Ar ₁ contains at least one donor atom, i.e. an atom with a lone pair of electrons, such as nitrogen, through which the cyclic group is connected to the metal by coordination; Ar ₂ contains at least one carbon atom, through which the cyclic group is connected to the metal; Ar ₁ and Ar ₂ are linked together by covalent bonds, and may each carry one or more substituent groups, and they may also be linked together by substituent groups; L' may be the same or different each time it appears, and is a bidentate chelating auxiliary 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 organic ligands may be selected from phenylpyridine derivatives or 7,8-benzoquinoline derivatives. All of these organic ligands may be substituted, for example, by alkyl chains or fluorine or silicon. The auxiliary ligand may be preferably selected from acetic acid acetone or picric acid.

The metal atom M is preferably a transition metal element, a lanthanide element or an actinide element; more preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Re, Cu, Ag, Ni, Co, W or Eu, and particularly preferably Ir, Au, Pt, W or Os.

In certain preferred embodiments, according to the organometallic complex of the present invention, the organic ligand L is selected from bidentate monovalent anionic ligands, bidentate divalent anionic ligands and bidentate zerovalent anionic ligands.

In a preferred embodiment, the bidentate monovalent anionic ligand is selected from any one of the following general formulas S1 to S15:

Wherein: R ¹ is a substituent, which, when it occurs multiple times, is independently selected from D, or F, or Cl, or Br, or I, or CN, or NO ₂ , or CF ₃ , or B(OR ² ) ₂ , or Si(R ² ) ₃ , or a straight-chain alkane, or an alkane ether, or an alkane thioether, or a branched-chain alkane, or a cycloalkane, and one or more non-adjacent methylene groups (CH ₂ ) in R ¹ may be replaced by R ³ ; R ³ , when it occurs multiple times, is independently selected from R ² C＝CR ² , C＝C, Si(R ² ) ₂ , Ge(R ² ) ₂ , Sn(R ² ) ₂ , C＝O, C＝S, C＝Se, C＝N(R ² ), O, S, -COO-, or CONR ² ; R ² is independently selected at each occurrence from H, D, or a straight-chain alkyl group having 1 to 20 C atoms, or an alkoxy group having 1 to 20 C atoms, or a thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, or a branched or cyclic alkoxy group having 3 to 20 C atoms, or a branched or cyclic thioalkoxy group having 3 to 20 C atoms, a silyl group, or a substituted keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, a CF ₃ groups, Cl, Br, F, cross-linkable groups, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms and an aryloxy or heteroaryloxy group having 5 to 40 ring atoms; the dotted line represents the bond directly connected to the metal element M; x is 0, 1 or 2, y is 0, 1, 2, 3 or 4, and z is 0, 1, 2 or 3.

In another preferred embodiment, the bidentate divalent anionic ligand is selected from any one of the following general formulas D1-D12:

Wherein R ¹ , x, y, and z have the same meanings as described above, and the dotted line represents the bond directly connected to the metal element M.

In another preferred embodiment, the bidentate zero-valent ligand is selected from any one of the following general formulas N1-N8:

Wherein R ¹ , x, y, and z have the same meanings as described above, u represents 0, 1, 2, 3, 4, or 5, and the dotted line represents a bond directly connected to the metal element M.

In a preferred embodiment, at least one of the above R ¹ comprises a free radical group.

In certain preferred embodiments, suitable stable organic free radical groups may be used in the organometallic complexes according to the present invention. The basis, materials, synthesis and application of stable organic free radical compounds can be easily found in professional books or papers, such as "Stable Radicals: Fundamentals and Applied Aspects of Odd-Electron Compounds Edited by Robin G. Hicks, 2010 John Wiley & Sons, Inc. ISBN: 978-0-470-77083-2", the contents of which are hereby incorporated herein by reference. In particular, the corresponding groups of stable organic free radical compounds suitable for use as organic free radical batteries can be used in the organometallic complexes according to the present invention.

In certain preferred embodiments, suitable organic free radical groups are selected from the following chemical formulas (1)-(3):

Wherein: Ar ₃ -Ar ₅ are independently selected from aryl or heteroaryl; R ₁ and R ₂ can be independently selected from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, and R ₁ and R ₂ can form a closed ring.

Suitable aryl or heteroaryl groups may be selected from, but are not limited to, anthracene, naphthalene, tetraphenyl, xanthene, phenanthrene, pyrene, indenopyrene, phenylene, decacyclopentene, hexaphenylene, fluorene, spirobifluorene, arylpyrene and the like.

In some preferred embodiments, suitable organic free radical groups are selected from the following groups:

Further information on the materials, synthesis and application of stable organic free radical compounds can be easily found in professional papers, such as Nishide et al. Electrochemical Society Interface 2005, 14, 32, Anamimoghadam et al. Org. Lett., Vol. 15, No. 12, 2013, Castellanos et al. Chem. Commun., 2010, 46, 5130-5132, Nesvadba et al. Chem. Mater. 2010, 22, 783-788, Hicks, Nature Chemistry Vol 3, 189 (2011), Morita et al., Nature Materials 10, 947 (2011), and U.S. Patent No. US20130199601, etc. The contents of the above-listed documents are hereby incorporated into this article for reference.

In another preferred embodiment, according to the organometallic complex of the present invention, the organometallic complex is selected from the general formula (II):

Wherein, A is selected from the general formula (III),

wherein ^L0 represents a bridging group selected from none, a single bridging group, a di-bridging group or a tri-bridging group; ^L1 and ^L2 are the same or different and are independently selected from a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or a silyl group, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate or an isothiocyanate, a hydroxyl group, a nitro group, _CF3 , Cl, Br, F, I, a crosslinkable group, or a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups; and MC is a metal complex.

In a preferred embodiment, according to the organometallic complex of the present invention, ^L1 and ^L2 in the general formula (II) are selected from substituted or unsubstituted aromatic groups or heteroaromatic groups having 5-20 ring atoms, preferably 5-15 ring atoms, more preferably 6-15 ring atoms, and most preferably 6-10 ring atoms, wherein ^L1 and ^L2 may be the same or different.

In a more preferred embodiment, according to the organometallic complex of the present invention, ^L1 and ^L2 in the general formula (II) are selected from fused aromatic groups or fused heterocyclic aromatic groups.

Aromatic groups refer to hydrocarbon groups containing at least one aromatic ring. Heteroaromatic groups refer to aromatic hydrocarbon groups containing at least one heteroatom. The heteroatom is preferably selected from Si, N, P, O, S and/or Ge, and is particularly preferably selected from Si, N, P, O and/or S. A condensed ring aromatic group refers to a ring of an aromatic group that can have two or more rings, in which two carbon atoms are shared by two adjacent rings, i.e., a condensed ring. A condensed heterocyclic aromatic group refers to a condensed ring aromatic hydrocarbon group containing at least one heteroatom. For the purposes of the present invention, aromatic groups or heteroaromatic groups include not only systems of aromatic rings, but also non-aromatic ring systems. Therefore, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, etc. are also considered to be aromatic groups or heterocyclic aromatic groups for the purposes of this invention. For the purposes of the present invention, fused aromatic or fused heteroaromatic ring systems include not only systems of aromatic or heteroaromatic groups, but also systems in which multiple aromatic or heteroaromatic groups may be interrupted by short non-aromatic units (<10% non-H atoms, preferably less than 5% non-H atoms, such as C, N or O atoms). Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, etc. are also considered fused aromatic ring systems for the purposes of the present invention.

Specifically, examples of the fused-ring aromatic group include naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof.

Specifically, examples of fused heterocyclic aromatic groups include benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, o-naphthylidene, quinoxaline, phenanthridine, primary pyridine, quinazoline, quinazolinone, and derivatives thereof.

In a preferred embodiment, ^L1 and ^L2 in the general formula (II) are independently selected from one or a combination of the following groups:

wherein: Y, when present, independently represents CR ¹ R ² , NR ¹ , O, S, SiR ¹ R ² , PR ¹ , P(═O)R ¹ , S═O, S(═O) ₂ or C═O; X, when present, independently represents CR ¹ or N; R ¹ and R ² , when present, independently represent H, D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, or a silyl group, or a keto group having 1 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 20 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF ₃ , Cl, Br, F, I, a cross-linkable group, or a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.

In some more preferred embodiments, ^L1 and ^L2 in the general formula (II) are selected from one or more combinations of the following structural groups:

wherein the H on the ring may be further substituted by _R3 , and R3, when present multiple _times , is independently selected from D, a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or a silyl group, or a substituted keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a _CF3 group, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 carbon atoms, or an aryloxy or heteroaryloxy group having 5 to 40 carbon atoms, or a combination of these groups, wherein two or more adjacent groups R ₃ may optionally form with one another a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system.

In a preferred embodiment, the organometallic complex of the present invention is selected from the following general formula, but not limited to:

Wherein X, Y, and A have the same meanings as above.

In a preferred embodiment, the organic ligand L or ^L in the general formula (III) is independently selected from one of the following groups or a combination thereof:

wherein: Ar ¹ is an unsubstituted or X ¹ substituted heteroaromatic hydrocarbon system containing at least one N; Ar ² is an unsubstituted or X ² substituted aromatic hydrocarbon or heteroaromatic hydrocarbon system containing at least one C; when X ¹ occurs multiple times, they are independently selected from H, F, Cl, Br, I, D, CN, NO ₂ , CF ₃ , B(OX ² ) ₂ , Si(X ² ) ₃ , straight chain alkanes, alkane ethers, alkane thioethers containing 1 to 10 carbon atoms, or branched alkanes, or cycloalkanes, alkane ethers or alkane thioether groups containing 3 to 10 carbon atoms, each of which can be substituted by one or more active groups X ² , and one or more non-adjacent methylene (CH ₂ ) can be replaced by the following groups, which include X ² C＝CX ² , C＝C, Si(X ² ) ₂ , Ge(X ² ) ₂ , Sn(X ² ) ₂ , C＝O, C＝S, C＝Se, C＝N(X ² ), O, S, -COO-, or CON X ^2, or a combination thereof, wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or N ₂ , or replaced by an aromatic amine containing one or more active groups X ² or an aromatic group and a heteroaromatic ring, or replaced by a substituted or unsubstituted carbazole; X ² in each occurrence is the same or different and is selected from H, D, aliphatic alkanes containing 1 to 10 carbon atoms, aromatic hydrocarbons, substituted or unsubstituted aromatic rings or heteroaromatic groups containing 5 to 10 ring atoms.

The dotted line represents a bond directly connected to the metal element M by a single bond, and the solid line represents a connection in the form of a single bond; Rr represents the above-mentioned organic free radical group.

In a more preferred embodiment, according to the organometallic complex of the present invention, Ar ¹ is selected from any one of the general formulas C1 to C3, wherein s is any integer from 0 to 4, t is any integer from 0 to 6, the dotted line indicates connection in the form of a single bond, and R ¹ is defined as above.

In a more preferred embodiment, according to the metal complex of the present invention, Ar ² is selected from any one of the general formulas C4 to C6, wherein s is any integer from 0 to 4, t is any integer from 0 to 6, the dotted line represents connection in the form of a single bond, the arrow represents a bond directly connected to the metal element M, and R ¹ is defined as above.

In a most preferred embodiment, the metal element M is selected from Ir.

Specific examples of suitable organometallic complexes according to the present invention are given below, and the structural formula shown may be further arbitrarily substituted:

In a particularly preferred embodiment, the organometallic complex according to the present invention is a luminescent material, and its luminescent wavelength is between 300 and 5000 nm, preferably between 350 and 4000 nm, and more preferably between 400 and 2000 nm. The luminescence referred to here refers to photoluminescence or electroluminescence. In certain preferred embodiments, the organometallic complex according to the present invention has a photoluminescence efficiency of ≥30%, preferably ≥40%, more preferably ≥50%, and most preferably ≥60%.

In certain embodiments, the organometallic complexes according to the present invention may also be non-emissive materials.

The present invention also relates to a polymer, wherein at least one repeating unit comprises a structure as shown in the above general formula M(L)n. In certain embodiments, the polymer is a non-conjugated polymer, wherein the structural unit as shown in the general formula M(L)n is on the side chain. In another preferred embodiment, the polymer is a conjugated polymer.

In certain embodiments, the polymer is a non-conjugated polymer, wherein the structure shown in the general formula M(L)n is on the side chain. In another preferred embodiment, the polymer is a conjugated polymer.

In a preferred embodiment, the synthesis method of the polymer is selected from SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.

In a preferred embodiment, the polymer according to the present invention has a glass transition temperature (Tg) ≥ 100°C, preferably ≥ 120°C, more preferably ≥ 140°C, more preferably ≥ 160°C, and most preferably ≥ 180°C.

In a preferred embodiment, the molecular weight distribution (PDI) of the polymer according to the present invention is preferably in the range of 1-5, more preferably 1-4, more preferably 1-3, even more preferably 1-2, and most preferably 1-1.5.

In a preferred embodiment, the weight average molecular weight (Mw) of the polymer according to the present invention is preferably in the range of 10,000-1,000,000, more preferably 50,000-500,000, more preferably 100,000-400,000, even more preferably 150,000-300,000, and most preferably 200,000-250,000.

The invention also relates to a mixture comprising at least one organometallic complex or polymer according to the invention and at least one other organic functional material.

Another organic functional material described herein includes hole (also called electric hole) injection material (HIM), hole transport material (HTM), hole blocking material (HBM), electron injection material (EIM), electron transport material (ETM), electron blocking material (EBM), organic host material (Host), singlet luminophore (fluorescent luminophore), thermally activated delayed fluorescence luminescent material (TADF), triplet luminophore (phosphorescent luminophore), especially luminescent metal organic complex, and organic dye. For example, various organic functional materials are described in detail in WO2010135519A1, US20090134784A1 and WO 2011110277A1, and the entire contents of these three patent documents are hereby incorporated herein by reference.

An object of the present invention is to provide a material solution for evaporation-type organic electronic devices.

In certain embodiments, the metal organic complex according to the present invention has a molecular weight of ≤1100 g/mol, preferably ≤1000 g/mol, very preferably ≤950 g/mol, more preferably ≤900 g/mol, and most preferably ≤800 g/mol.

Another object of the present invention is to provide a material solution for printed organic electronic devices.

In certain embodiments, the organometallic complex according to the present invention has a molecular weight of ≥700 g/mol, preferably ≥900 g/mol, preferably ≥1000 g/mol, and most preferably ≥1100 g/mol.

In other embodiments, the solubility of the organometallic complex according to the present invention in toluene at 25° C. is ≥10 mg/ml, preferably ≥15 mg/ml, and most preferably ≥20 mg/ml.

The present invention further relates to a composition or ink comprising an organometallic complex or polymer according to the present invention and at least one organic solvent.

When used in printing processes, the viscosity and surface tension of the ink are important parameters. The appropriate surface tension parameters of the ink are suitable for a specific substrate and a specific printing method.

In a preferred embodiment, the surface tension of the ink according to the present invention at operating temperature or at 25°C is approximately in the range of 19 dyne/cm to 50 dyne/cm; more preferably in the range of 22 dyne/cm to 35 dyne/cm; and most preferably in the range of 25 dyne/cm to 33 dyne/cm.

In another preferred embodiment, the viscosity of the ink according to the present invention at the working temperature or 25° C. is about 1 cps to 100 cps; preferably 1 cps to 50 cps; more preferably 1.5 cps to 20 cps; and most preferably 4.0 cps to 20 cps. The composition thus formulated will facilitate inkjet printing.

The viscosity can be adjusted by different methods, such as by selecting a suitable solvent and the concentration of the functional material in the ink. The ink containing the metal organic complex or polymer according to the present invention can facilitate people to adjust the printing ink in an appropriate range according to the printing method used. Generally, the weight ratio of the functional material contained in the composition according to the present invention is in the range of 0.3% to 30wt%, preferably in the range of 0.5% to 20wt%, more preferably in the range of 0.5% to 15wt%, more preferably in the range of 0.5% to 10wt%, and most preferably in the range of 1% to 5wt%.

In some embodiments, according to the ink of the present invention, the at least one organic solvent is selected from aromatic or heteroaromatic based solvents, in particular aliphatic chain/ring substituted aromatic solvents, or aromatic ketone solvents, or aromatic ether solvents.

Examples of solvents suitable for the present invention include, but are not limited to: aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, 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, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 1 , 3-dipropoxybenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.; ketone-based solvents: 1-tetralone, 2-tetralone, 2-(phenylepoxy)tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and their derivatives, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4- Methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2,6,8-trimethyl-4-nonanone, fenchone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, phorone, di-n-amyl ketone; aromatic ether solvents: 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethyl ether, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethyl Oxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-tert-butylanisole, trans-p-propenylanisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, amyl ether c-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; ester solvents: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, etc.

Further, according to the ink of the present invention, the at least one solvent can be selected from: aliphatic ketones, for example, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, 2,6,8-trimethyl-4-nonanone, phorone, di-n-amyl ketone, etc.; or aliphatic ethers, for example, 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, etc.

In some other embodiments, the printing ink further comprises another organic solvent. Examples of another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetralin, decalin, indene and/or mixtures thereof.

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 composition in the embodiment of the present invention may include 0.01 to 20 wt % of the organometallic complex or polymer or a mixture thereof according to the present invention, preferably 0.1 to 15 wt %, more preferably 0.2 to 10 wt %, and most preferably 0.25 to 5 wt % of the metal organic complex or a mixture thereof.

The present invention also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices, and particularly preferably a preparation method by printing or coating.

Among them, suitable printing or coating techniques include (but are not limited to) inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, twist roller printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slit extrusion coating, etc. The preferred ones are inkjet printing, nozzle printing and gravure printing. The solution or suspension may further include one or more components such as surfactant compounds, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, etc., for adjusting viscosity, film-forming properties, improving adhesion, etc. For printing technology and its related requirements for related solutions, such as solvents and concentrations, viscosity, etc., please refer to "Handbook of Print Media: Technologies and Production Methods" edited by Helmut Kipphan for detailed information, ISBN 3-540-67326-1.

Based on the above-mentioned organometallic complex or polymer, the present invention also provides an application of the above-mentioned organometallic complex or polymer, that is, the organometallic complex or polymer is applied to an organic electronic device, and the organic electronic device can be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, an organic spin electronic device, an organic spin valve, a photodiode, an organic sensor and an organic plasmon emitting diode (Organic Plasmon Emitting Diode), etc., and organic electroluminescent devices such as OLED, OLEEC, and organic light emitting field effect transistor are particularly preferred. Preferably, the organometallic complex or polymer is used in the light emitting layer of the electroluminescent device.

The present invention further relates to an organic electronic device, comprising at least one of the above-mentioned organic metal complexes or polymers. Generally, such an organic electronic device comprises at least one cathode, one anode and a functional layer between the cathode and the anode, wherein the functional layer comprises at least one of the above-mentioned organic metal complexes or polymers. The organic electronic device can 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, organic lasers, organic spin electronic devices, organic spin valves, photodiodes, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diodes), etc., and organic electroluminescent devices such as OLEDs, OLEECs, and organic light emitting field effect transistors are particularly preferred; other particularly preferred organic spin electronic devices or organic spin valves.

In certain particularly preferred embodiments, the electroluminescent device comprises a light-emitting layer, wherein the light-emitting layer comprises one of the organic metal complexes or polymers, or comprises one of the organic metal complexes or polymers and a phosphorescent light-emitting body, or comprises one of the organic metal complexes or polymers and a host material, or comprises one of the organic metal complexes or polymers, a phosphorescent light-emitting body and a host material.

The electroluminescent device described above, especially OLED, comprises a substrate, an anode, at least one light-emitting layer, and a cathode.

The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting device. For example, see Bulovic et al. Nature 1996, 380, p29, and Gu et al., Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. It is best that the substrate has a smooth surface. Substrates without surface defects are particularly ideal. In a preferred embodiment, the substrate is flexible and can be selected from polymer films or plastics, and its glass transition temperature Tg is above 150°C, preferably above 200°C, more preferably above 250°C, and preferably above 300°C. Examples of suitable flexible substrates include poly (ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

The anode may include a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into the hole injection layer (HIL) or the hole transport layer (HTL) or the light-emitting layer. In a preferred embodiment, the absolute value of the difference between the work function of the anode and the HOMO energy level or valence band energy level of the light-emitting body in the light-emitting layer or the p-type semiconductor material as the HIL or HTL or the electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and 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), etc. Other suitable anode materials are known and can be easily selected for use by a person of ordinary skill in the art. The anode material can 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), etc. In some embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

The cathode may include 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 a preferred embodiment, the absolute value of the difference between the work function of the cathode and the LUMO energy level or conduction band energy level of the luminophore in the light-emitting layer or the n-type semiconductor material as the electron injection layer (EIL) or the electron transport layer (ETL) or the hole blocking layer (HBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials that can be used as cathodes of OLEDs may be used as cathode materials for the device of the present invention. Examples of cathode materials include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material can 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), etc.

OLEDs may also include other 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), and a hole blocking layer (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1, and WO2011110277A1, and the entire contents of these three patent documents are hereby incorporated herein by reference.

In a preferred embodiment, in the light-emitting device according to the present invention, the light-emitting layer thereof is prepared by the composition according to the present invention.

According to the light emitting device of the present invention, the light emission wavelength is between 300 and 5000 nm, preferably between 350 and 4000 nm, and more preferably between 400 and 2000 nm.

The present invention also relates to the application of the organic electronic device according to the present invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

The present invention also relates to electronic devices comprising the organic electronic device according to the present invention, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

Specific embodiments

1. Organometallic complexes and their synthesis

Synthesis Example 1: Synthesis of Complex Ir1

Synthesis route of complex Ir1:

Synthesis of compound 1a: 2-(4-bromophenyl)pyridine (0.69 g, 3.0 mmol), diborane (0.81 g, 3.2 mmol), potassium acetate (0.9 g, 9.0 mmol), and pd(dppf)2Cl2 (0.11 g, 0.15 mmol) were placed in a dry two-necked bottle, and the mixture was evacuated and filled with nitrogen for three cycles. Then 70 mL of 1,4-dioxane was added, and the reaction was stirred at 85°C for 14 hours. The mixture was cooled to room temperature, and water and dichloromethane were added for extraction. The organic phase was concentrated and filtered through a column with dichloromethane: petroleum ether = 5:1 to obtain 0.59 g of a yellow solid with a yield of 70%.

Synthesis of compound 1b: 1a (0.56 g, 2 mmol), tri(2,4,6-trichlorophenyl)methane (0.80 g, 2 mmol), tetrakis(triphenylphosphine)palladium (0.12 g, 0.1 mmol), potassium phosphate (10.2 g, 48 mmol) were placed in a dry two-necked bottle, and the vacuum was evacuated and nitrogen was filled for three cycles. Then 36 mL of toluene, 12 mL of ethanol and 24 mL of water were added, and the reaction was stirred at 95 ° C for 48 hours. The mixture was cooled to room temperature, water was added, extracted with dichloromethane, concentrated, and purified by column with dichloromethane: petroleum ether = 3:1 to obtain 0.40 g of white powder solid with a yield of 30%.

Synthesis of compound 1c: 1b (4.87 g, 7.3 mmol) and hydrated iridium trichloride (1.05 g, 3 mmol) were placed in a dry two-necked bottle, and the mixture was evacuated and filled with nitrogen for three cycles. Then, a mixed solution of 36 mL of ethylene glycol monoethyl ether and 12 mL of water was added, and the mixture was stirred at 110°C for 24 hours. The mixture was cooled to room temperature, filtered, washed with n-hexane, and dried to obtain 3.9 g of a yellow solid with a yield of 70%. The solid was directly used for the next step without further purification.

Synthesis of compound 1d: 1c (2.47 g, 0.79 mmol), sodium carbonate (0.41 g, 3.8 mmol), and acetylacetone (0.58 mL, 5.6 mmol) were placed in a dry two-necked bottle, and the solution was evacuated and filled with nitrogen for three cycles. Then, 15 mL of ethylene glycol monoethyl ether was added, and the reaction was stirred at 100°C for 24 hours. The solution was cooled to room temperature, water was added to the solution, and the solution was filtered. The filter cake was dissolved with dichloromethane, filtered through silica gel, concentrated, dissolved with a small amount of dichloromethane, and 1.54 g of solid was precipitated with petroleum ether. The yield was 60%.

Synthesis of complex Ir1: 1d (0.16 g, 0.1 mmol) and potassium tert-butoxide (0.05 g, 0.4 mmol) were placed in a dry two-necked bottle, and the vacuum was evacuated and nitrogen was filled for three cycles. Then, 10 mL of dry tetrahydrofuran was added under nitrogen flow, and the mixture was heated to 80°C in a dark environment. The mixture was stirred for 12 hours, cooled to room temperature, and tetrachlorobenzoquinone (0.13 g, 0.54 mmol) was added. The reaction was continued in a dark environment for 1.5 hours. The organic phase was concentrated and filtered through a column with dichloromethane: petroleum ether = 3:1 to obtain 0.13 g of a yellow solid with a yield of 80%.

Synthesis Example 2: Synthesis of Complex Ir2

Synthesis route of complex Ir2:

Synthesis of compound 2a: 1d (1.63 g, 1 mmol) and 1b (1.33 g, 2 mmol) were placed in a dry two-necked bottle, and then 50 mL of glycerol was added. The mixture was vacuumed and filled with nitrogen for three cycles. The mixture was stirred at 170°C for 24 hours, cooled to room temperature, water was added to the solution, and the solution was filtered. The filter cake was recrystallized with a mixed solution of dichloromethane and petroleum ether to obtain 0.55 g of solid with a yield of 25%.

Synthesis of complex Ir2: Place 2a (0.22 g, 0.1 mmol) and potassium tert-butoxide (0.07 g, 0.6 mmol) in a dry two-necked bottle, evacuate and fill with nitrogen for three cycles, then add 10 mL of dry tetrahydrofuran under nitrogen flow, heat to 80°C in a dark environment, stir and react for 12 hours, cool to room temperature, add tetrachlorobenzoquinone (0.19 g, 0.81 mmol), continue to react in a dark environment for 1.5 hours, concentrate the organic phase, and filter it with dichloromethane: petroleum ether = 3:1 to obtain 0.19 g of yellow solid with a yield of 85%.

Synthesis Example 3: Synthesis of Complex Ir3

Synthesis route of complex Ir3:

Synthesis of compound 3a: 2-phenylpyridine (11.32 g, 72.9 mmol) and hydrated iridium trichloride (10.48 g, 30 mmol) were placed in a dry two-necked bottle, and the mixture was evacuated and filled with nitrogen for three cycles. Then, a mixed solution of 360 mL of ethylene glycol monoethyl ether and 120 mL of water was added, and the mixture was stirred at 110°C for 24 hours. The mixture was cooled to room temperature, filtered, washed with n-hexane, and dried to obtain 15.6 g of a yellow solid with a yield of 80%. The mixture was directly used for the next step without further purification.

Synthesis of compound 3b: 3a (2.0 g, 1.87 mmol) was placed in a dry single-mouth bottle, and then a mixed solution of 200 mL of dichloromethane and 10 mL of methanol was added to dissolve it. Silver trifluoromethanesulfonate (1.0 g, 3.92 mmol) was then added to the mixture, and then stirred at room temperature for 8 hours. The mixture was filtered and the filtrate was dried to obtain 2.18 g of a yellow solid with a yield of 90%.

Synthesis of compound 3c: 3b (2.59 g, 4 mmol) and 1b (7.75 g, 11.6 mmol) were placed in a dry two-necked bottle, and the mixture was evacuated and filled with nitrogen for three cycles. Then 300 mL of ethanol was added and the mixture was stirred and refluxed for 24 hours. The mixture was cooled to room temperature, filtered and dried to obtain 3.27 g of a yellow solid with a yield of 70%.

Synthesis of complex Ir3: 3c (0.12 g, 0.1 mmol) and potassium tert-butoxide (0.02 g, 0.2 mmol) were placed in a dry two-necked bottle, and the vacuum was evacuated and nitrogen was filled for three cycles. Then, 10 mL of dry tetrahydrofuran was added under nitrogen flow, and the mixture was heated to 80°C in a dark environment. The reaction was stirred for 12 hours, cooled to room temperature, and tetrachlorobenzoquinone (0.06 g, 0.27 mmol) was added. The reaction was continued in a dark environment for 1.5 hours. The organic phase was concentrated and filtered through a column with dichloromethane: petroleum ether = 3:1 to obtain 0.09 g of a yellow solid with a yield of 80%.

Synthesis Example 4: Synthesis of Complex Ir4

Synthesis route of complex Ir4:

Synthesis of compound 4a: 2-(3-bromophenyl)pyridine (0.69 g, 3.0 mmol), diborane (0.81 g, 3.2 mmol), potassium acetate (0.9 g, 9.0 mmol), and pd(dppf)2Cl2 (0.11 g, 0.15 mmol) were placed in a dry two-necked bottle, and the mixture was evacuated and filled with nitrogen for three cycles. Then 70 mL of 1,4-dioxane was added, and the reaction was stirred at 85 °C for 14 hours. The mixture was cooled to room temperature, and water and dichloromethane were added for extraction. The organic phase was concentrated and filtered through a column with dichloromethane: petroleum ether = 5:1 to obtain 0.63 g of a yellow solid with a yield of 75%.

Synthesis of compound 4b: In a dry two-necked bottle were placed 4a (0.56 g, 2 mmol), tris(2,4,6-trichlorophenyl)methane (0.80 g, 2 mmol), tetrakis(triphenylphosphine)palladium (0.12 g, 0.1 mmol), and potassium phosphate (10.2 g, 48 mmol). The mixture was evacuated and nitrogen was filled for three cycles. Then, 36 mL of toluene, 12 mL of ethanol, and 24 mL of water were added. The mixture was stirred at 95 °C for 48 hours, cooled to room temperature, water was added, extracted with dichloromethane, concentrated, and purified by column with dichloromethane: petroleum ether = 3:1 to obtain 0.60 g of a white powder solid with a yield of 45%.

Synthesis of compound 4c: 4b (4.87 g, 7.3 mmol) and hydrated iridium trichloride (1.05 g, 3 mmol) were placed in a dry two-necked bottle, and the mixture was evacuated and filled with nitrogen for three cycles. Then, a mixed solution of 36 mL of ethylene glycol monoethyl ether and 12 mL of water was added, and the mixture was stirred at 110°C for 24 hours. The mixture was cooled to room temperature, filtered, washed with n-hexane, and dried to obtain 3.9 g of a yellow solid with a yield of 70%. The solid was directly used for the next step without further purification.

Synthesis of compound 4d: 4c (2.47 g, 0.79 mmol), sodium carbonate (0.41 g, 3.8 mmol), and acetylacetone (0.58 mL, 5.6 mmol) were placed in a dry two-necked bottle, and the solution was evacuated and filled with nitrogen for three cycles. Then, 15 mL of ethylene glycol monoethyl ether was added, and the reaction was stirred at 100°C for 24 hours. The solution was cooled to room temperature, water was added to the solution, and the solution was filtered. The filter cake was dissolved with dichloromethane, filtered through silica gel, concentrated, dissolved with a small amount of dichloromethane, and 1.28 g of solid was precipitated with petroleum ether. The yield was 50%.

Synthesis of complex Ir4: 4d (0.16 g, 0.1 mmol) and potassium tert-butoxide (0.05 g, 0.4 mmol) were placed in a dry two-necked bottle, and the vacuum was evacuated and nitrogen was filled for three cycles. Then, 10 mL of dry tetrahydrofuran was added under nitrogen flow, and the mixture was heated to 80°C in a dark environment. The reaction was stirred for 12 hours, cooled to room temperature, and tetrachlorobenzoquinone (0.13 g, 0.54 mmol) was added. The reaction was continued in a dark environment for 1.5 hours. The organic phase was concentrated and filtered through a column with dichloromethane: petroleum ether = 3:1 to obtain 0.15 g of a yellow solid with a yield of 90%.

Synthesis Example 5: Synthesis of Complex Ir5

Synthesis route of complex Ir5:

Synthesis of compound 5a: 4d (1.63 g, 1 mmol) and 4b (1.33 g, 2 mmol) were placed in a dry two-necked bottle, and then 50 mL of glycerol was added. The mixture was vacuumed and filled with nitrogen for three cycles. The mixture was stirred at 170°C for 24 hours, cooled to room temperature, water was added to the solution, and the solution was filtered. The filter cake was recrystallized from a mixed solution of dichloromethane and petroleum ether to obtain 0.66 g of solid with a yield of 30%.

Synthesis of complex Ir5: 5a (0.22 g, 0.1 mmol) and potassium tert-butoxide (0.07 g, 0.6 mmol) were placed in a dry two-necked bottle, and the vacuum was evacuated and nitrogen was filled for three cycles. Then, 10 mL of dry tetrahydrofuran was added under nitrogen flow, and the mixture was heated to 80°C in a dark environment and stirred for 12 hours. After cooling to room temperature, tetrachlorobenzoquinone (0.19 g, 0.81 mmol) was added, and the reaction was continued in a dark environment for 1.5 hours. The organic phase was concentrated and filtered through a column with dichloromethane: petroleum ether = 3:1 to obtain 0.20 g of a yellow solid with a yield of 85%.

Synthesis Example 6: Synthesis of Complex Ir6

Synthesis route of complex Ir6:

Synthesis of compound 6a: 3b (2.59 g, 4 mmol) and 4b (7.75 g, 11.6 mmol) were placed in a dry two-necked bottle, and the mixture was evacuated and filled with nitrogen for three cycles. Then 300 mL of ethanol was added, and the mixture was stirred and refluxed for 24 hours. The mixture was cooled to room temperature, filtered, and dried to obtain 2.80 g of a yellow solid with a yield of 60%.

Synthesis of complex Ir6: 6a (0.12 g, 0.1 mmol) and potassium tert-butoxide (0.02 g, 0.2 mmol) were placed in a dry two-necked bottle, and the vacuum was evacuated and nitrogen was filled for three cycles. Then, 10 mL of dry tetrahydrofuran was added under nitrogen flow, and the mixture was heated to 80°C in a dark environment. The reaction was stirred for 12 hours, cooled to room temperature, and tetrachlorobenzoquinone (0.06 g, 0.27 mmol) was added. The reaction was continued in a dark environment for 1.5 hours. The organic phase was concentrated and filtered through a column with dichloromethane: petroleum ether = 3:1 to obtain 0.10 g of a yellow solid with a yield of 85%.

Synthesis Example 7: Synthesis of Complex Ir7

Synthesis route of complex Ir7:

Synthesis of compound 7a: 4-bromo-2-phenylpyridine (0.69 g, 3.0 mmol), diborane (0.81 g, 3.2 mmol), potassium acetate (0.9 g, 9.0 mmol), and pd(dppf)2Cl2 (0.11 g, 0.15 mmol) were placed in a dry two-necked bottle, and the mixture was evacuated and filled with nitrogen for three cycles. Then 70 mL of 1,4-dioxane was added, and the reaction was stirred at 85°C for 14 hours. The mixture was cooled to room temperature, and water and dichloromethane were added for extraction. The organic phase was concentrated and filtered through a column with dichloromethane: petroleum ether = 5:1 to obtain 0.59 g of a yellow solid with a yield of 70%.

Synthesis of compound 7b: In a dry two-necked flask were placed 7a (0.56 g, 2 mmol), tri(2,4,6-trichlorophenyl)methane (0.80 g, 2 mmol), tetrakis(triphenylphosphine)palladium (0.12 g, 0.1 mmol), and potassium phosphate (10.2 g, 48 mmol). The mixture was evacuated and nitrogen was filled for three cycles. Then, 36 mL of toluene, 12 mL of ethanol, and 24 mL of water were added. The mixture was stirred at 95 °C for 48 hours, cooled to room temperature, water was added, extracted with dichloromethane, concentrated, and purified by column with dichloromethane: petroleum ether = 3:1 to obtain 0.60 g of a white powder solid with a yield of 45%.

Synthesis of compound 7c: 7b (4.87 g, 7.3 mmol) and hydrated iridium trichloride (1.05 g, 3 mmol) were placed in a dry two-necked flask, and the mixture was evacuated and filled with nitrogen for three cycles. Then, a mixed solution of 36 mL of ethylene glycol monoethyl ether and 12 mL of water was added, and the mixture was stirred at 110°C for 24 hours. The mixture was cooled to room temperature, filtered, washed with n-hexane, and dried to obtain 3.9 g of a yellow solid with a yield of 70%. The solid was directly used for the next step without further purification.

Synthesis of compound 7d: 7c (2.47 g, 0.79 mmol), sodium carbonate (0.41 g, 3.8 mmol), and acetylacetone (0.58 mL, 5.6 mmol) were placed in a dry two-necked bottle, and the solution was evacuated and filled with nitrogen for three cycles. Then, 15 mL of ethylene glycol monoethyl ether was added, and the reaction was stirred at 100°C for 24 hours. The solution was cooled to room temperature, water was added to the solution, and the solution was filtered. The filter cake was dissolved with dichloromethane, filtered through silica gel, concentrated, dissolved with a small amount of dichloromethane, and 1.54 g of solid was precipitated with petroleum ether. The yield was 60%.

Synthesis of complex Ir7: 7d (0.16 g, 0.1 mmol) and potassium tert-butoxide (0.05 g, 0.4 mmol) were placed in a dry two-necked bottle, and the vacuum was evacuated and nitrogen was filled for three cycles. Then, 10 mL of dry tetrahydrofuran was added under nitrogen flow, and the mixture was heated to 80°C in a dark environment. The mixture was stirred for 12 hours, cooled to room temperature, and tetrachlorobenzoquinone (0.13 g, 0.54 mmol) was added. The reaction was continued in a dark environment for 1.5 hours. The organic phase was concentrated and filtered through a column with dichloromethane: petroleum ether = 3:1 to obtain 0.13 g of a yellow solid with a yield of 80%.

Synthesis Example 8: Synthesis of Complex Ir8

Synthesis route of complex Ir8:

Synthesis of compound 8a: 7d (1.63 g, 1 mmol) and 7b (1.33 g, 2 mmol) were placed in a dry two-necked bottle, and then 50 mL of glycerol was added. The mixture was vacuumed and filled with nitrogen for three cycles. The mixture was stirred at 170°C for 24 hours, cooled to room temperature, water was added to the solution, and the solution was filtered. The filter cake was recrystallized from a mixed solution of dichloromethane and petroleum ether to obtain 1.06 g of solid with a yield of 48%.

Synthesis of complex Ir8: Place 8a (0.22 g, 0.1 mmol) and potassium tert-butoxide (0.07 g, 0.6 mmol) in a dry two-necked bottle, evacuate and fill with nitrogen for three cycles, then add 10 mL of dry tetrahydrofuran under nitrogen flow, heat to 80°C in a dark environment, stir and react for 12 hours, cool to room temperature, add tetrachlorobenzoquinone (0.19 g, 0.81 mmol), continue to react in a dark environment for 1.5 hours, concentrate the organic phase, and filter it with dichloromethane: petroleum ether = 3:1 to obtain 0.20 g of a yellow solid with a yield of 85%.

Synthesis Example 9: Synthesis of Complex Ir9

Synthesis route of complex Ir9:

Synthesis of compound 9a: 3b (2.59 g, 4 mmol) and 4b (7.75 g, 11.6 mmol) were placed in a dry two-necked bottle, and the mixture was evacuated and filled with nitrogen for three cycles. Then 300 mL of ethanol was added, and the mixture was stirred and refluxed for 24 hours. The mixture was cooled to room temperature, filtered, and dried to obtain 2.80 g of a yellow solid with a yield of 60%.

Synthesis of complex Ir9: Place 9a (0.12 g, 0.1 mmol) and potassium tert-butoxide (0.02 g, 0.2 mmol) in a dry two-necked bottle, evacuate and fill with nitrogen for three cycles, then add 10 mL of dry tetrahydrofuran under nitrogen flow, heat to 80°C in a dark environment, stir and react for 12 hours, cool to room temperature, add tetrachlorobenzoquinone (0.06 g, 0.27 mmol), continue to react in a dark environment for 1.5 hours, concentrate the organic phase, and filter it with dichloromethane: petroleum ether = 3:1 to obtain 0.10 g of a yellow solid with a yield of 85%.

Synthesis Example 10: Synthesis of Complex Ir10

Synthesis route of complex Ir10:

Synthesis of compound 10a: 5-bromo-2-phenylpyridine (0.69 g, 3.0 mmol), diborane (0.81 g, 3.2 mmol), potassium acetate (0.9 g, 9.0 mmol), and pd(dppf)2Cl2 (0.11 g, 0.15 mmol) were placed in a dry two-necked bottle, and the mixture was evacuated and filled with nitrogen for three cycles. Then 70 mL of 1,4-dioxane was added, and the reaction was stirred at 85°C for 14 hours. The mixture was cooled to room temperature, and water and dichloromethane were added for extraction. The organic phase was concentrated and filtered through a column with dichloromethane: petroleum ether = 5:1 to obtain 0.51 g of a yellow solid with a yield of 60%.

Synthesis of compound 10b: In a dry two-necked bottle were placed 10a (0.56 g, 2 mmol), tris(2,4,6-trichlorophenyl)methane (0.80 g, 2 mmol), tetrakis(triphenylphosphine)palladium (0.12 g, 0.1 mmol), and potassium phosphate (10.2 g, 48 mmol). The mixture was evacuated and nitrogen was filled for three cycles. Then, 36 mL of toluene, 12 mL of ethanol, and 24 mL of water were added. The mixture was stirred at 95 °C for 48 hours, cooled to room temperature, water was added, extracted with dichloromethane, concentrated, and purified by column with dichloromethane: petroleum ether = 3:1 to obtain 0.60 g of a white powder solid with a yield of 45%.

Synthesis of compound 10c: 10b (4.87 g, 7.3 mmol) and hydrated iridium trichloride (1.05 g, 3 mmol) were placed in a dry two-necked bottle, and the mixture was evacuated and filled with nitrogen for three cycles. Then, a mixed solution of 36 mL of ethylene glycol monoethyl ether and 12 mL of water was added, and the mixture was stirred at 110°C for 24 hours. The mixture was cooled to room temperature, filtered, washed with n-hexane, and dried to obtain 3.9 g of a yellow solid with a yield of 70%. The solid was directly used for the next step without further purification.

Synthesis of compound 10d: 10c (2.47 g, 0.79 mmol), sodium carbonate (0.41 g, 3.8 mmol), and acetylacetone (0.58 mL, 5.6 mmol) were placed in a dry two-necked bottle, and the solution was evacuated and filled with nitrogen for three cycles. Then, 15 mL of ethylene glycol monoethyl ether was added, and the reaction was stirred at 100°C for 24 hours. The solution was cooled to room temperature, water was added, and the solution was filtered. The filter cake was dissolved with dichloromethane, filtered through silica gel, concentrated, dissolved with a small amount of dichloromethane, and 1.54 g of solid was precipitated with petroleum ether. The yield was 60%.

Synthesis of complex Ir10: 10d (0.16 g, 0.1 mmol) and potassium tert-butoxide (0.05 g, 0.4 mmol) were placed in a dry two-necked bottle, and the vacuum was evacuated and nitrogen was filled for three cycles. Then, 10 mL of dry tetrahydrofuran was added under a nitrogen flow, and the mixture was heated to 80°C in a dark environment. The mixture was stirred for 12 hours, cooled to room temperature, and tetrachlorobenzoquinone (0.13 g, 0.54 mmol) was added. The reaction was continued in a dark environment for 1.5 hours. The organic phase was concentrated and filtered through a column with dichloromethane: petroleum ether = 3:1 to obtain 0.13 g of a yellow solid with a yield of 80%.

Synthesis Example 11: Synthesis of Complex Ir11

Synthesis route of complex Ir11:

Synthesis of compound 11a: 10d (1.63 g, 1 mmol) and 10b (1.33 g, 2 mmol) were placed in a dry two-necked bottle, and then 50 mL of glycerol was added. The mixture was vacuumed and filled with nitrogen for three cycles. The mixture was stirred at 170°C for 24 hours, cooled to room temperature, water was added to the solution, and the solution was filtered. The filter cake was recrystallized with a mixed solution of dichloromethane and petroleum ether to obtain 0.82 g of solid with a yield of 37%.

Synthesis of complex Ir11: Place 11a (0.22 g, 0.1 mmol) and potassium tert-butoxide (0.07 g, 0.6 mmol) in a dry two-necked bottle, evacuate and fill with nitrogen for three cycles, then add 10 mL of dry tetrahydrofuran under nitrogen flow, heat to 80°C in a dark environment, stir and react for 12 hours, cool to room temperature, add tetrachlorobenzoquinone (0.19 g, 0.81 mmol), continue to react in a dark environment for 1.5 hours, concentrate the organic phase, and filter it with dichloromethane: petroleum ether = 3:1 to obtain 0.21 g of yellow solid with a yield of 89%.

Synthesis Example 12: Synthesis of Complex Ir12

Synthesis route of complex Ir12:

Synthesis of compound 12a: 3b (2.59 g, 4 mmol) and 10b (7.75 g, 11.6 mmol) were placed in a dry two-necked bottle, and the mixture was evacuated and filled with nitrogen for three cycles. Then 300 mL of ethanol was added, and the mixture was stirred and refluxed for 24 hours. The mixture was cooled to room temperature, filtered, and dried to obtain 2.66 g of a yellow solid with a yield of 57%.

Synthesis of complex Ir12: Place 12a (0.12 g, 0.1 mmol) and potassium tert-butoxide (0.02 g, 0.2 mmol) in a dry two-necked flask, evacuate and fill with nitrogen for three cycles, then add 10 mL of dry tetrahydrofuran under nitrogen flow, heat to 80°C in a dark environment, stir and react for 12 hours, cool to room temperature, add tetrachlorobenzoquinone (0.06 g, 0.27 mmol), continue to react in a dark environment for 1.5 hours, concentrate the organic phase, and filter it with dichloromethane: petroleum ether = 3:1 to obtain 0.11 g of a yellow solid with a yield of 94%.

Synthesis Example 13: Synthesis of Complex Pt1

Synthesis route of complex Pt1:

Synthesis of compound 13c: 10b (4.87 g, 7.3 mmol) and potassium tetrachloroplatinate (II) (2.53 g, 6.1 mmol) were placed in a dry two-necked bottle, and the mixture was evacuated and filled with nitrogen for three cycles. Then, a mixed solution of 36 mL of ethylene glycol monoethyl ether and 12 mL of water was added, and the mixture was stirred at 110°C for 24 hours. The mixture was cooled to room temperature, filtered, washed with n-hexane, and dried to obtain 6.6 g of a yellow solid with a yield of 60%. The solid was directly used for the next step without further purification.

Synthesis of compound 13d: 13c (1.42 g, 0.79 mmol), sodium carbonate (0.21 g, 1.9 mmol), and acetylacetone (0.29 mL, 2.8 mmol) were placed in a dry two-necked bottle, and the solution was evacuated and filled with nitrogen for three cycles. Then, 15 mL of ethylene glycol monoethyl ether was added, and the reaction was stirred at 100°C for 24 hours. The solution was cooled to room temperature, water was added to the solution, and the solution was filtered. The filter cake was dissolved with dichloromethane, filtered through silica gel, concentrated, dissolved with a small amount of dichloromethane, and petroleum ether was added to precipitate 0.38 g of solid, with a yield of 50%.

Synthesis of complex Pt1: 13d (0.10 g, 0.1 mmol) and potassium tert-butoxide (0.02 g, 0.2 mmol) were placed in a dry two-necked bottle, and the vacuum was evacuated and nitrogen was filled for three cycles. Then, 10 mL of dry tetrahydrofuran was added under a nitrogen flow, and the mixture was heated to 80°C in a dark environment. The reaction was stirred for 12 hours, cooled to room temperature, and tetrachlorobenzoquinone (0.06 g, 0.27 mmol) was added. The reaction was continued in a dark environment for 1.5 hours. The organic phase was concentrated and filtered through a column with dichloromethane: petroleum ether = 3:1 to obtain 0.09 g of a yellow solid with a yield of 95%.

Synthesis Example 14: Synthesis of Complex Pt2

Synthesis route of complex Pt2:

Synthesis of compound 14d: 13c (1.42 g, 0.79 mmol), sodium carbonate (0.21 g, 1.9 mmol), and 2-picolinic acid (0.34 g, 2.8 mmol) were placed in a dry two-necked bottle, and the solution was evacuated and filled with nitrogen for three cycles. Then, 15 mL of ethylene glycol monoethyl ether was added, and the reaction was stirred at 100°C for 24 hours. The solution was cooled to room temperature, water was added, and the solution was filtered. The filter cake was dissolved with dichloromethane, filtered through silica gel, concentrated, dissolved with a small amount of dichloromethane, and petroleum ether was added to precipitate 0.43 g of solid, with a yield of 55%.

Synthesis of complex Pt2: 14d (0.10 g, 0.1 mmol) and potassium tert-butoxide (0.02 g, 0.2 mmol) were placed in a dry two-necked bottle, and the vacuum was evacuated and nitrogen was filled for three cycles. Then, 10 mL of dry tetrahydrofuran was added under a nitrogen flow, and the mixture was heated to 80°C in a dark environment. The reaction was stirred for 12 hours, cooled to room temperature, and tetrachlorobenzoquinone (0.06 g, 0.27 mmol) was added. The reaction was continued in a dark environment for 1.5 hours. The organic phase was concentrated and filtered through a column with dichloromethane: petroleum ether = 3:1 to obtain 0.09 g of a yellow solid with a yield of 95%.

Synthesis Example 15: Synthesis of Complex Pt3

Synthesis route of complex Pt3:

Synthesis of compound 15d: 13c (1.42 g, 0.79 mmol), sodium carbonate (0.21 g, 1.9 mmol), and 2,2,6,6-tetramethyl-3,5-heptanedione (0.52 g, 2.8 mmol) were placed in a dry two-necked bottle, and the solution was evacuated and filled with nitrogen for three cycles. Then, 15 mL of ethylene glycol monoethyl ether was added, and the reaction was stirred at 100°C for 24 hours. The solution was cooled to room temperature, water was added to the solution, and the solution was filtered. The filter cake was dissolved with dichloromethane, filtered through silica gel, concentrated, dissolved with a small amount of dichloromethane, and 0.37 g of solid was precipitated with petroleum ether. The yield was 45%.

Synthesis of complex Pt3: 15d (0.10 g, 0.1 mmol) and potassium tert-butoxide (0.02 g, 0.2 mmol) were placed in a dry two-necked bottle, and the vacuum was evacuated and nitrogen was filled for three cycles. Then, 10 mL of dry tetrahydrofuran was added under a nitrogen flow, and the mixture was heated to 80°C in a dark environment, stirred for reaction for 12 hours, cooled to room temperature, and tetrachlorobenzoquinone (0.06 g, 0.27 mmol) was added. The reaction was continued in a dark environment for 1.5 hours, and the organic phase was concentrated and filtered through a column with dichloromethane: petroleum ether = 3:1 to obtain 0.10 g of a yellow solid with a yield of 95%.

2. Electron paramagnetic resonance spectra of organometallic complexes

Test conditions: The iridium complex free radical Ir3 (i.e. the above-mentioned synthetic complex Ir3) was tested in dichloromethane solution at room temperature, and the test instrument model was BRUKE EMXPLUS electron paramagnetic resonance (EPR) spectrometer. Its g factor was 2, which clearly showed that the metal complex Ir3 was a free radical compound.

It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims (13)

1. An organometallic complex having the general formula M (L) n, wherein M is a metal atom, L is an organic ligand, L may be the same or different at each occurrence and is bonded or coordinated to M through one or more positions, n is any integer from 1 to 6, characterized in that at least one L comprises an organic radical group.

2. The organometallic complex according to claim 1, characterized in that M is selected from transition metal elements or lanthanides or actinides.

3. Organometallic complex according to claim 1 or 2, characterized in that M is selected from Ir, pt, pd, au, rh, ru, os, re, cu, ag, ni, co, W or Eu.

4. An organometallic complex according to any of claims 1-3, characterized in that at least one of said L is a bidentate monovalent anionic ligand and is selected from any of the following formulae S1 to S15:

wherein:

R ¹ is a substituent, and is selected from D, or F, or Cl, or Br, or I, or CN, or NO, independently of each other ₂ Or CF (CF) ₃ OR B (OR) ² ) ₂ Or Si (R) ² ) ₃ Or a linear alkane, or an alkane ether, or an alkane thioether, or a branched alkane, or a cycloalkane, and R ¹ One or more non-adjacent methylene groups of (a) may be substituted by R ³ Replacement;wherein at least one R ¹ Is substituted by a radical group;

R ³ at multiple occurrences, are independently selected from R ² C＝CR ² ,C＝C,Si(R ² ) ₂ ,Ge(R ² ) ₂ ,Sn(R ² ) ₂ ,C＝O,C＝S,C＝Se,C＝N(R ² ) O, S, -COO-, or CONR ² ；

R ² Each occurrence is independently selected from H, D, or a linear alkyl group having 1 to 20C atoms, or an alkoxy group having 1 to 20C atoms, or a thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl group having 3 to 20C atoms, or a branched or cyclic alkoxy group having 3 to 20C atoms, or a branched or cyclic thioalkoxy group having 3 to 20C atoms, a silyl group, or a substituted keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, a CF group ₃ A group, cl, br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms and one or more of an aryloxy or heteroaryloxy group having 5 to 40 ring atoms;

the dotted line represents a bond directly connected to the metal element M;

x is any integer from 0 to 2, y is any integer from 0 to 4, and z is any integer from 0 to 3.

5. The organometallic complex according to any of claims 1 to 4, characterized in that the organic radical group is selected from the following chemical formula (1) -chemical formula (3):

wherein: ar (Ar) ₃ -Ar ₅ Independently selected from aryl or heteroaryl; r is R ₁ And R is ₂ Can be selected independently of one another from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, and R ₁ And R is ₂ A closed loop may be formed.

6. The organometallic complex according to any of claims 1 to 5, characterized in that the organic radical group is selected from the following groups.

7. The organometallic complex according to any of claims 1 to 6, characterized in that at least one of the L is selected from the following structural formulae:

wherein,,

Ar ¹ is unsubstituted or X ¹ A substituted heteroaromatic hydrocarbon system containing at least one N;

Ar ² Is unsubstituted or X ² A substituted aromatic or heteroaromatic hydrocarbon system;

X ¹ at multiple occurrences, independently selected from H, F, cl, br, I, D, CN, NO ₂ 、CF ₃ 、B(OX ² ) ₂ 、Si(X ² ) ₃ Linear alkanes, alkane ethers, alkane sulfides or branched alkanes or cycloalkanes containing 1 to 10 carbon atoms, alkane ether or alkane sulfide groups containing 3 to 10 carbon atoms, each X ¹ The radicals may each be substituted by one or more reactive groups X ² Substituted, and one or more non-adjacent methylene groups may be replaced by groups comprising X ² C＝CX ² 、C＝C、Si(X ² ) ₂ 、Ge(X ² ) ₂ 、Sn(X ² ) ₂ 、C＝O、C＝S、C＝Se、C＝N(X ² ) O, S, COO and CONX ² One or a combination of them, wherein one or more H atoms may be replaced by D, F, cl, br, I, CN or N ₂ Substituted by, or containing, one or more reactive groups X ² Or one aromatic group and heteroaromatic ring substituted aromatic amine, or substituted or unsubstituted carbazole;

X ² the same or different at each occurrence is selected from H, D, aliphatic alkanes containing 1 to 10 carbon atoms, aromatic hydrocarbons, substituted or unsubstituted aromatic rings or heteroaromatic groups containing 5 to 10 ring atoms;

the dotted line represents a bond directly connected to M by a single bond;

rr represents the organic radical group.

8. The organometallic complex according to claim 7, characterized in that 1) the Ar ¹ Selected from any one of the general formulas C1 to C3, wherein s is any integer from 0 to 4, t is any integer from 0 to 6, the dotted line represents a single bond, R ¹ R in the same manner as in claim 4 ¹ The method comprises the steps of carrying out a first treatment on the surface of the And/or 2) the Ar ² Selected from any one of the general formulae C4 to C6, wherein s is any integer from 0 to 4, t is any integer from 0 to 6, the dotted line represents a bond in the form of a single bond, the arrow represents a bond directly to M, R ¹ R in the same manner as in claim 4 ¹ 。

9. A polymer comprising at least one repeating unit, wherein the repeating unit comprises a structural unit represented by the general formula M (L) n in claim 1.

10. A mixture comprising at least one organometallic complex according to any one of claims 1 to 8 or a polymer according to claim 9, and at least one further organic functional material, which can be selected from hole-injecting materials, hole-transporting materials, electron-injecting materials, electron-blocking materials, hole-blocking materials, luminescent materials, host materials and organic dyes.

11. A composition comprising at least one organometallic complex according to any of claims 1 to 8 or a polymer according to claim 9, and at least one organic solvent.

12. An organic electronic device comprising at least one organometallic complex according to any of claims 1 to 8 or a polymer according to claim 9 or a mixture according to claim 10.

13. The organic electronic device of claim 12, wherein the organic electronic device is selected from the group consisting of an organic light emitting diode, an organic photovoltaic cell, an organic light emitting cell, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, an organic spintronic device, an organic spin valve, a photodiode, an organic sensor, and an organic plasmon emitting diode.