WO2018108110A1 - Metal organic complex and use thereof, mixture, and organic electronic device - Google Patents

Abstract

Disclosed are a metal organic complex and the use thereof, a mixture, and an organic electronic device. The structure of the metal organic complex is as shown by general formula (1), and the definitions of the symbols in the general formula (I) are the same as defined in the description.

Description

Metal organic complexes and their applications, mixtures, organic electronic devices

This application claims priority to Chinese Patent Application No. 201611148194.5, entitled "A Metal Organic Complex and Its Application in Electronic Devices", filed on December 13, 2016, the entire contents of which are hereby incorporated by reference. The citations are incorporated herein by reference.

Technical field

The invention relates to the technical field of organic photoelectric materials, in particular to a metal organic complex and an application, a mixture thereof and an organic electronic device.

Background technique

In flat panel display and lighting applications, Organic Light-Emitting Diode (OLED) has low cost, light weight, low operating voltage, high brightness, color adjustability, wide viewing angle, easy assembly onto flexible substrates, and The advantage of low energy consumption has thus become the most promising display technology. In order to improve the luminous efficiency of organic light emitting diodes, various systems based on fluorescent and phosphorescent materials have been developed. An organic light-emitting diode using a fluorescent material has high reliability, but its internal electroluminescence quantum efficiency is limited to 25% under electric field excitation. In contrast, since the branch ratio of the singlet excited state and the triplet excited state of the excitons is 1:3, an organic light emitting diode using a phosphorescent material can achieve an internal luminescence quantum efficiency of almost 100%. For small molecule OLEDs, the triplet excitation is effectively obtained by doping the center of the heavy metal, thereby increasing the spin-orbit coupling, and thus the inter-system to triplet state.

Metal ruthenium (III)-based complexes are a class of materials widely used in high-efficiency OLEDs with high efficiency and stability. Baldo et al. reported the use of fac-tris(2-phenylpyridine)ruthenium(III)[Ir(ppy)3] as a phosphorescent material, 4,4'-N,N'-dicarbazole-biphenyl (4 , 4'-N, N'-diarbazole-biphenyl) (CBP) is a high quantum efficiency OLED of matrix material (Appl. Phys. Lett. 1999, 75, 4). Another example of a phosphorescent luminescent material is the sky blue complex bis[2-(4',6'-difluorophenyl)pyridine-N,C2]-pyridinium ruthenate (III) (FIrpic), which is doped to high The triplet energy matrix exhibits an extremely high photoluminescence quantum efficiency of approximately 60% in solution and almost 100% in solid film (Appl. Phys. Lett. 2001, 79, 2082). Although ruthenium (III) systems based on 2-phenylpyridine and its derivatives have been used in large quantities for the preparation of OLEDs, phosphorescent luminescent materials containing other metal centers with these ligands have remained largely unexplored.

Despite increasing interest in phosphorescent materials, particularly metal complexes with heavy metal centers, most efforts have focused on the use of cerium (III), platinum (II), copper (I) and cerium (II). Other metal centers are rarely noticed. Unlike isoelectronic platinum (II) complexes, which are known to exhibit high-energy optical properties, examples of luminescent gold (III) complexes are rarely reported, which may be derived from the low energy of gold (III) metal centers. The presence of the dd coordination field (LF) and the electrophilicity of the gold (III) metal center. One way to improve the luminous efficiency of gold (III) complexes is to introduce strong σ-donor ligands, such as the stable gold (III) aryl compounds first discovered and synthesized by Yam et al., even at room temperature. Interesting photoluminescence properties (J. Chem. Soc., Dalton Trans. 1993, 1001). Another interesting donor is an alkynyl group. Although the optical rotation properties of the gold (I) alkynyl complex have been extensively studied, the chemistry of the gold (III) alkynyl group has been largely ignored, with one exception: 6-benzyl-2,2'-bipyridine. Synthesis of alkyne fund (III) compounds (J. Chem. Soc. Dalton Trans. 1999, 2823), but its optical rotation properties have not been studied. Yam et al. disclose the synthesis of a series of bis-cyclometalated acetylene fund (III) compounds using various strong σ-donor alkynyl ligands, all of which exhibit in various media at room and low temperatures. Very strong luminescent properties (J. Am. Chem. Soc. 2007, 129, 4350). In addition, the external quantum efficiency of OLEDs prepared using these luminescent gold (III) compounds as phosphorescent dopant materials was 5.5%. These luminescent gold (III) compounds contain a tridentate ligand and at least one strong σ-donor group coordinated to the gold (III) metal center. Since then, Yam et al. have reported a new class of phosphorescent materials for metallized acetylene fund (III) complexes (J. Am. Chem. Soc. 2010, 132, 14273). The optimized vapor-deposited OLED achieves a current efficiency of 11.5% EQE and 37.4 cd A-1. This indicates that the acetylene fund (III) complex is a promising luminescent material. However, the stability of such compounds needs to be improved.

In order to improve the stability of the gold (III) complex and the lifetime of the device without reducing the luminous efficiency, one solution is to The tridentate ligand and the monodentate coordination combine to form a tetradentate ligand with more coordinate bonds to obtain a more stable complex. Tetradentate ligands have been investigated for use in other transition metals such as platinum (II) (US9224963B2), palladium (II) (Chem. Sci. 2016, 7, 6083) and the like. Such tetradentate coordination metal complexes also have good performance in OLED applications. However, in the case of gold (III), which is an electronic structure, this research field is relatively small. Moreover, on the synthetic route, the gold (III) complex of the tridentate ligand is a precursor that requires mercury as a precursor (Chem. Commun. 2005, 2906), which is detrimental to the environment. The tetradentate ring metallized gold (III) complex can make the complex more stable, increase the rigidity of the molecule, and make the luminous efficiency higher. In principle, the tetradentate ring metallized gold (III) complex does not require the use of a mercury compound as a precursor in the synthesis.

Summary of the invention

In accordance with various embodiments of the present application, there is provided a metal organic complex and its use, mixture, organic electronic device that addresses one or more of the problems involved in the background art.

A metal organic complex having a structure as shown in the general formula (1):

among them,

M is a metal atom and M is selected from gold or palladium;

L is selected from the group consisting of two bridges;

Ar ¹ and Ar ^{2 are} independently selected from an aromatic group having 5 to 20 ring atoms, a heteroaromatic group having 5 to 20 ring atoms, or a non-aromatic ring system having 5 to 20 ring atoms; Ar ¹ And Ar ² independently have a substituent R ¹ or R ² ;

Ar ³ and Ar ⁴ independently have an aromatic group having 5 to 20 ring atoms, a heteroaromatic group having 5 to 20 ring atoms, or a non-aromatic ring system having 5 to 20 ring atoms; Ar ³ and Ar ⁴ independently has a substituent R ³ or R ⁴ ;

R ¹ , R ² , R ³ and R ^{4 are} independently selected from hydrogen, deuterium, a halogen atom or a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and 1 a linear alkenyl group of -20 carbon atoms, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a heteroaromatic group of 1 to 20 carbon atoms or a non-aromatic ring system of 1 to 20 carbon atoms.

A polymer in which at least one repeating unit comprises the above metal organic complex.

A mixture comprising at least one organic functional material and the above metal organic or the above polymer; the organic functional material is selected from the group consisting of a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, an electron blocking material, and an empty Hole blocking material, illuminant, host material or doping material.

A composition comprising an organic solvent and the above metal organic or the above polymer or a mixture thereof.

Use of the above metal organic or the above polymer or the above mixture or the above composition in the preparation of an organic electronic device.

An organic electronic device comprising the above metal organic complex or the above polymer or a mixture thereof.

Details of one or more embodiments of the invention are set forth in the accompanying drawings and description below. Other features, objects, and advantages of the invention will be apparent from the description and appended claims.

detailed description

The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to The invention is defined.

In this context, compositions, printing inks, and inks have the same meaning and are interchangeable. In this context, host materials, matrix materials, Host, and Matrix materials have the same meaning and are interchangeable. Herein, metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and are interchangeable.

The structure of the metal organic complex of one embodiment is as shown in the general formula (1):

among them,

M is a metal atom and M is selected from gold or palladium;

L is selected from the group consisting of two bridges;

Ar ¹ and Ar ^{2 are} independently selected from an aromatic group having 5 to 20 ring atoms, a heteroaromatic group having 5 to 20 ring atoms, or a non-aromatic ring system having 5 to 20 ring atoms; Ar ¹ And Ar ² independently have a substituent R ¹ or R ² ;

Ar ³ and Ar ⁴ independently have an aromatic group having 5 to 20 ring atoms, a heteroaromatic group having 5 to 20 ring atoms, or a non-aromatic ring system having 5 to 20 ring atoms; Ar ³ and Ar ⁴ independently has a substituent R ³ or R ⁴ ;

R ¹ , R ² , R ³ and R ^{4 are} independently selected from hydrogen, deuterium, a halogen atom or a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and 1 a linear alkenyl group of -20 carbon atoms, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a heteroaromatic group of 1 to 20 carbon atoms or a non-aromatic ring system of 1 to 20 carbon atoms.

It should be noted that Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may be the same or different when they occur multiple times independently. R ¹ , R ² , R ³ and R ⁴ independently may be the same or different when they occur multiple times. R ¹ , R ² , R ³ and R ⁴ may be bonded at any position of the aromatic ring or the heteroaromatic ring.

The metal organic complex is used in an OLED, especially as a light-emitting layer doping material, which can provide higher device light-emitting properties and device lifetime. The novel metal-organic complexes of this type contain coordination bonds to the center of four pairs of metal atoms, so that the entire complex has better chemical, optical, electrical, and thermal stability, and the four coordination bonds increase the entire The rigidity of the complex can effectively improve the light-emitting properties of the complex material, which provides the possibility of improving the photoelectric performance and device stability of the related device. On the synthetic route, mercury compounds are not required as precursors, thus making the synthesis process simpler and environmentally friendly. In addition, through device structure optimization, changing the concentration of metal complexes in the matrix, can achieve the best device performance, easy to achieve high efficiency, high brightness and high stability of OLED devices, providing better material options for full color display and lighting applications. .

In one of the embodiments, M is selected from the group consisting of gold. From the point of view of the heavy atom effect, gold (Au) is used as the central metal M of the above metal organic complex. This is because gold is chemically stable and has a significant heavy atomic effect that results in high luminous efficiency.

In each occurrence of M, the same or different is a bridge or a second bridge or a triple bridge or a quad bridge group, which is connected to Ar ¹ or Ar ² or Ar ³ or Ar ⁴ by a single bond or a double bond.

In one embodiment, L is selected from the group consisting of a linear alkyl group having 0 to 10 carbon atoms, a branched alkyl group having 0 to 10 carbon atoms, a linear alkenyl group having 0 to 10 carbon atoms, and having Branched alkenyl group of 0-10 carbon atoms, alkyl ether group of 0-10 carbon atoms, O, S, S=O, SO ₂ , N(R), B(R), Si(R) ₂ , Ge(R) ₂ , P(R), P(=O)R, P(R) ₃ , Sn(R) ₂ , C(R) ₂ , C=O, C=S, C=Se, C=N(R) ₂ , C=C(R) ₂ , an aromatic ring system containing 5-20 carbon atoms or a heteroaromatic ring system containing 4-20 carbon atoms; R is the same or different, is selected From hydrogen, hydrazine, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 1 to 20 carbon atoms, having 1 a branched alkenyl group of 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a heteroaromatic group having 1 to 20 carbon atoms or having 1 a non-aromatic ring system of -20 carbon atoms.

Further, R is selected from an aromatic ring system having 5 to 15 carbon atoms or a heteroaromatic ring system having 4 to 15 carbon atoms. In one embodiment, R is selected from the group consisting of an aromatic ring system having 5 to 10 carbon atoms or a heteroaromatic ring system having 4 to 10 carbon atoms. In one embodiment, L is selected from the group consisting of a linear alkyl group having 0 to 5 carbon atoms, a branched alkyl group having 0 to 5 carbon atoms, a linear alkenyl group having 0 to 5 carbon atoms, and having A branched alkenyl group of 0 to 5 carbon atoms, an alkyl ether group having 0 to 5 carbon atoms. Further, L is selected from a linear alkyl group having 0 to 2 carbon atoms, a branched alkyl group having 0 to 2 carbon atoms, a linear alkenyl group having 0 to 2 carbon atoms, and having 0 to 2 A branched alkenyl group of a carbon atom, an alkyl ether group having 0 to 2 carbon atoms.

In one embodiment, L is selected from any of the following groups:

Wherein #1 indicates bonding to any position of Ar ¹ ; #2 indicates bonding to any position of Ar ² ; Z contains at least one nitrogen, oxygen, carbon, silicon, boron, sulfur or phosphorus atom R ¹⁸ -R ^{20 are} independently selected from H, D, a halogen atom, CN, NO ₂ , CF ₃ , B(OR) ₂ , Si(R) ₃ , a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 1 to 20 carbon atoms, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether having 1 to 20 carbon atoms a group having an aromatic group of 1 to 20 carbon atoms, a heteroaromatic group having 1 to 20 carbon atoms or a non-aromatic ring system having 1 to 20 carbon atoms; the R is selected from the group consisting of hydrogen and hydrogen, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms A branched alkenyl group, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a heteroaromatic group having 1 to 20 carbon atoms or having 1 to 20 carbon atoms Non-aromatic ring system.

In one embodiment, L is selected from any of the following groups.

Wherein R ₃ , R ₄ , R ₅ and R ₆ are the same as defined for R ¹ and R ^{2 described} above; the dashed bond represents a bond to Ar ¹ or Ar ² .

In one embodiment, L is selected from any of the following groups.

In one embodiment, L is selected from any of the following groups.

In one embodiment, Ar ¹ , Ar ² , Ar ³ or Ar ^{4 is} selected from the group consisting of a non-aromatic ring system having 5-20 ring atoms which are unsubstituted or substituted by R. It has a triplet energy level that can increase the metal complex, thereby facilitating the technical effect of obtaining a green or blue light emitter.

For the purposes of the present invention, non-aromatic ring systems contain from 1 to 10 carbon atoms in the ring system and include not only saturated but also partially unsaturated cyclic systems which may be unsubstituted or single or multiple by the group R. Instead, the groups R may be the same or different in each occurrence. In one embodiment, the non-aromatic ring system contains from 1 to 3 carbon atoms in the ring system. In one embodiment, the non-aromatic ring system may also contain one or more heteroatoms. Wherein, the hetero atom may be selected from one or more of Si, N, P, O, S, and Ge. In one embodiment, the hetero atom is selected from one or more of Si, N, P, O, and S. These may, for example, be cyclohexyl- or piperidine-like systems or ring-like octadiene ring systems. The term also applies to fused non-aromatic ring systems. In one embodiment, the non-aromatic ring system contains from 1 to 6 carbon atoms in the ring system.

In one embodiment, R is selected from the group consisting of: (1) a C1-C10 alkyl group, wherein the C1-C10 alkyl group may refer to the group: methyl, ethyl, n-propyl, isopropyl, cyclopropane. Base, 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, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl , hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl (2) a C1-C10 alkoxy group, wherein the C1-C10 alkoxy group may be a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, or a sec-butyl group. Oxyl, tert-butoxy or 2-methylbutoxy; (3) C2-C10 aryl or heteroaryl, which may be monovalent or divalent depending on the use, and in each case may also be the above-mentioned group, and R ¹⁰ may be substituted by any desired position of the aromatic or heteroaromatic group Connection. In one embodiment, the C2-C10 aryl or heteroaryl group is selected from the group consisting of benzene, naphthalene, anthracene, quinone, indoline, fluorene, fluorene, fluoranthene, butyl, pentane, benzene. And hydrazine, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, thiopurine, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, Isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole , oxazole, imidazole, benzimidazole, naphthimidazole, phenamimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphtazole, oxazole , phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzoxazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, diazepine 1,5-naphthyridine, carbazole, benzoporphyrin, 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- Diazole, 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, anthracene, pteridine, hydrazine or benzothiadiazole. For the purposes of the present invention, aromatic and heteroaromatic ring systems are considered to be especially in addition to the above-mentioned aryl and heteroaryl groups, but also to biphenylene, benzene terphenyl, anthracene, spirobifluorene, dihydrogen. Phenanthrene, tetrahydroanthracene and cis or trans fluorene.

In one embodiment, Ar ¹ , Ar ² , Ar ³ and Ar ^{4 are} independently selected from an aromatic group having 5 to 20 ring atoms or a heteroaromatic group having 5 to 20 ring atoms. In one embodiment, Ar ¹ , Ar ² , Ar ³ and Ar ^{4 are} independently selected from an aromatic group having 5 to 18 ring atoms or a heteroaromatic group having 5 to 18 ring atoms. In one embodiment, Ar ¹ , Ar ² , Ar ³ and Ar ^{4 are} independently selected from an aromatic group having 5 to 12 ring atoms or a heteroaromatic group having 5 to 12 ring atoms. In one embodiment, at least one of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ is selected from heteroaromatic groups containing one ring heteroatom N. Further, at least two of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are selected from heteroaromatic groups containing one ring hetero atom N.

An aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system. A heteroaromatic group refers to a hydrocarbon group (containing a hetero atom) comprising at least one heteroaromatic ring, including a monocyclic group and a polycyclic ring system. These multi-ring rings can There are two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. At least one of these rings of the polycyclic ring is aromatic or heteroaromatic. For the purposes of the present invention, aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also multiple aryl or heteroaryl groups may also be interrupted by short non-aromatic units (<10%). Non-H atoms, such as C, N or O atoms). Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc., are also considered to be aromatic ring systems for the purposes of the present invention. In one embodiment, a plurality of aryl or heteroaryl groups may also be interrupted by short non-aromatic units (less than 5% non-H atoms).

Specifically, the aromatic group may be selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene or derivatives thereof.

Specifically, examples of the heteroaromatic group may include furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, anthracene, Carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine , pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone or derivatives thereof.

In one embodiment, Ar ¹ -Ar ^{4 are} independently selected from any of the following groups:

Wherein A ¹ -A ^{8 are} independently selected from CR 3 or N;

Y ¹ is selected from _{CR 4 R 5, SiR 4 R} 5, NR 3, C (= O), S , or O;

R ₃ , R ₄ , R _{5 are} independently selected from H, D, a linear alkyl group having 1 to 20 C atoms, an alkoxy group having 1 to 20 C atoms, and sulfur having 1 to 20 C atoms. Alkoxy group, branched or cyclic alkyl group having 3 to 20 C atoms, branched or cyclic alkoxy group having 3 to 20 C atoms, having 3 to 20 C atoms a branched or cyclic thioalkoxy group, a branched or cyclic silyl group having 3 to 20 C atoms, a substituted keto group having 1 to 20 C atoms, having 2 to 20 C atom alkoxycarbonyl groups, 7 to 20 C atom aryloxycarbonyl groups, cyano groups, carbamoyl groups, haloformyl groups, formyl groups , isocyano group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, crosslinkable a group, one or more of a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, an aryloxy group having 5 to 40 ring atoms, or a heteroaryloxy group At least one of R ₃ , R ₄ , and R ₅ and the structural group The bonded ring forms a monocyclic or polycyclic aliphatic or aromatic ring, or at least two of R ₃ , R ₄ , R ₅ are bonded to each other to form a monocyclic or polycyclic aliphatic or aromatic ring.

In one embodiment, Ar ¹ -Ar ^{4 are} independently selected from any of the following groups. Among them, H on the ring can be arbitrarily substituted.

In one embodiment, Ar ¹ and Ar ^{2 are} independently selected from any of the following groups:

Wherein P represents a bond to any position of Ar ³ or Ar ⁴ ;

X ¹ -X ¹⁸ independently contains at least one nitrogen, oxygen, carbon, silicon, boron, sulfur or phosphorus atom;

R ⁵ -R ^{7 are} independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. a linear alkenyl group, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms Heteroaromatic group or a non-aromatic ring system having 1-20 carbon atoms;

Y is selected from the group consisting of two bridged groups.

In one embodiment, Y is selected from the group consisting of a linear alkyl group having 0 to 2 carbon atoms, a branched alkyl group having 0 to 2 carbon atoms, a linear alkenyl group having 0 to 2 carbon atoms, and having Branched alkenyl group of 0-2 carbon atoms, alkyl ether group of 0-2 carbon atoms, O, S, S=O, SO ₂ , N(R), B(R), Si(R) ₂ , Ge(R) ₂ , P(R), P(=O)R, P(R) ₃ , Sn(R) ₂ , C(R) ₂ , C=O, C=S, C=Se, C=N(R) ₂ , C=C(R) ₂ , an aromatic ring system containing 5-20 carbon atoms or a heteroaromatic ring system containing 4-20 carbon atoms. R is the same or different and is selected from the group consisting of hydrogen, deuterium, a halogen atom, hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and a linear alkenyl group of 1 to 20 carbon atoms, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, A heteroaromatic group having 1 to 20 carbon atoms or a non-aromatic ring system having 1 to 20 carbon atoms.

In one embodiment, Y is selected from a non-aromatic group selected from any of the groups recited above for L.

In one embodiment, Ar ¹ and Ar ^{2 are} independently selected from any of the following groups:

Wherein R ^{8 -} R ^{10 are} independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and having 1 to 20 carbons. a linear alkenyl group of an atom, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, having 1 to 20 A heteroaromatic group of a carbon atom or a non-aromatic ring system having 1 to 20 carbon atoms.

In one embodiment, Ar ³ and Ar ^{4 are} independently selected from any of the following groups:

Wherein, Q represents Ar ¹ or Ar with any of the ^2-position is bonded;

X ¹⁹ -X ³¹ independently comprise at least one nitrogen, oxygen, carbon, silicon, boron, sulfur or phosphorus atom;

R ¹¹ -R ^{13 are} independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. a linear alkenyl group, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms Heteroaromatic groups or non-aromatic ring systems having 1-20 carbon atoms.

In one embodiment, Ar ³ and Ar ^{4 are} independently selected from any of the following groups:

Wherein R ^{11 to} R ^{13 are} independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. a linear alkenyl group of an atom, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, having 1 to 20 A heteroaromatic group of a carbon atom or a non-aromatic ring system having 1 to 20 carbon atoms.

In one of the embodiments, the structure of the metal organic complex is as shown in the formula (I-1) or (I-18):

Wherein R ^{21 -} R ^{31 are} independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. a linear alkenyl group of an atom, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, having 1 to 20 a heteroaromatic group of a carbon atom or a non-aromatic ring system having 1 to 20 carbon atoms; R ²¹ -R ³¹ may be bonded at any position of an aromatic group or a heteroaromatic group; X ³² -X ³⁸ independently Contains at least one nitrogen, oxygen, carbon, silicon, boron, sulfur or phosphorus atom.

In one embodiment, at least one of X ³² -X ³⁸ is selected from a nitrogen atom.

Specific examples of suitable metal organic complexes according to the present invention are given below, but are not limited thereto.

In one of the embodiments, the metal organic complex according to the invention is a luminescent material having an emission wavelength between 300 and 1000 nm. Further, the metal organic complex has an emission wavelength of between 350 and 900 nm. In one embodiment, the metal organic complex has an emission wavelength between 400 and 800 nm. The luminescence referred to herein means photoluminescence or electroluminescence. In one embodiment, the photoluminescence efficiency of the metal organic complex is > 30%. In one embodiment, the photoluminescence efficiency of the metal organic complex is > 40%. In one of the embodiments, the photoluminescence efficiency of the metal organic complex is ≥ 50%. In one embodiment, the photoluminescence efficiency of the metal organic complex is > 60%.

In one embodiment, the metal organic complex according to the invention may also be a non-luminescent material.

The use of the above metal organic complexes in polymers. The use of the above metal organic complexes in a mixture. The use of the above metal organic complex organic electronic device.

The polymer of one embodiment wherein at least one of the repeating units comprises the above metal organic complex. In one of the embodiments, the polymer is a non-conjugated high polymer in which the structural unit represented by the formula (1) is on the side chain. In another embodiment, the polymer is a conjugated polymer.

The mixture of an embodiment comprises at least one organic functional material and the above metal organic complex. Organic functional materials are selected from the group consisting of holes (also known as holes) injection or transport materials (HIM/HTM), hole blocking materials (HBM), electron injecting or transporting materials (EIM/ETM), electron blocking materials (EBM), organic Host material, singlet emitter (fluorescent emitter), heavy emitter (phosphorescent emitter) or organic thermal excitation delayed fluorescent material (TADF material). The organic thermal excitation delayed fluorescent material may be a light emitting organic metal complex. Various organic functional materials are described in detail in, for example, WO 2010135519 A1, US 2009 0 134 784 A1, and WO 2011110277 A1, the entire contents of each of which are hereby incorporated by reference. The organic functional material may be a small molecule or a high polymer material.

The term "small molecule" as defined herein refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there are no repeating structures in small molecules. The molecular weight of the small molecule is ≤3000 g/mol. Further, the molecular weight of the small molecule is ≤2000 g/mol. Further, the molecular weight of the small molecule is ≤1500 g/mol.

The high polymer, that is, the polymer, contains a homopolymer, a copolymer, and a block copolymer. Further, in the present invention, the high polymer also contains a dendrimer. For the synthesis and application of the tree, see [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.].

A conjugated polymer is a high polymer whose backbone is mainly composed of sp2 hybrid orbitals of C atoms. Famous examples are: polyacetylene polyacetylene and poly(phenylene vinylene). The C atom in the main chain can also be substituted by other non-C atoms, and is still considered to be a conjugated polymer when the sp ² hybrid on the main chain is interrupted by some natural defects. Further, in the present invention, the conjugated high polymer further comprises an aryl amine, an aryl phosphine and other heteroarmotics, and an organometallic complexes in the main chain. )Wait.

In one embodiment, the metal organic complex is present in an amount of from 0.01 to 30% by weight. In one embodiment, the metal organic complex is present in an amount of from 0.1 to 20% by weight. In one embodiment, the metal organic complex is present in an amount of 0.2. Up to 20% by weight. In one embodiment, the metal organic complex is present in an amount from 2 to 15% by weight.

In one embodiment, the mixture comprises the above metal organic complex and a triplet matrix material. At this time, the metal organic complex is used as a guest (phosphorescent emitter), and the weight percentage of the metal organic complex is ≤ 30% by weight. In one embodiment, the weight percent of the metal organic complex is < 20 wt%. Further, the weight percentage of the metal organic complex is ≤15% by weight.

In one embodiment, the mixture comprises the above metal organic complex, one triplet matrix material, and another triplet emitter.

In one embodiment, the mixture comprises the above metal organic complex and a thermally activated delayed fluorescent luminescent material (TADF).

The following is a detailed description of the triplet matrix material, the triplet emitter and the TADF material (but is not limited thereto). 1. Triplet Host Material (Triplet Host):

The example of the triplet host material is not particularly limited, and any metal complex or organic compound may be used as the host as long as its triplet energy is higher than that of the illuminant, particularly the triplet illuminant or the phosphorescent illuminant. Examples of metal complexes that can be used as the triplet host include, but are not limited to, the following general structure:

M is a metal; (Y ³ -Y ⁴ ) is a two-dentate ligand, Y ³ and Y ^{4 are} independently selected from C, N, O, P or S; L is an ancillary ligand; m is an integer, The value is from 1 to the maximum coordination number of this metal; m+n is the maximum coordination number of this metal.

In one embodiment, the metal complex that can be used as the triplet host has the following form:

Wherein (O-N) is a two-dentate ligand in which the metal is coordinated to the O and N atoms.

In one embodiment, M is selected from the group consisting of Ir or Pt.

Examples of the organic compound which can be used as the host of the triplet state are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenyl, benzo, fluorene; or a compound containing an aromatic heterocyclic group such as dibenzothiophene. , dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, carbazole, pyridinium, pyrrole dipyridine, pyrazole, imidazole, Triazoles, oxazoles, thiazoles, oxadiazoles, triazoles, dioxazoles, thiadiazoles, pyridines, pyridazines, pyrimidines, pyrazines, triazines, oxazines, oxazines, dioxazins, Anthracene, benzimidazole, carbazole, oxazole, dibenzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, o-naphthyridine, quinazoline, quinoxaline, naphthalene , anthracene, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furopyridine, benzothienopyridine, thienopyridine, benzoselenopyridine and selenophene And dipyridine; or a group containing a 2 to 10 ring structure, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic Ring group, and at least one of the following groups coupled together directly or through another, such as an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, chain structural unit and the aliphatic cyclic group. Wherein each Ar may be further substituted, and the substituent is selected from hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl or heteroaryl.

In one embodiment, the triplet host material is selected from the group consisting of at least one of the following groups:

Wherein R ¹ -R ^{7 are} independently selected from hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl or heteroaryl, when they are aryl or heteroaryl When they are the same as Ar ¹ and Ar ² described above; n is selected from 0, ¹ , ^2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, ¹³ , 14, 15, ¹⁶ , 17, 18, 19 or 20; X1-X8 is selected from CH or N, and X ^{9 is} selected from CR ¹ R ² or NR ¹ .

Examples of suitable triplet host materials are listed in the table below.

2. Triplet emitter (Triplet Emitter)

Triplet emitters are also known as phosphorescent materials. In a preferred embodiment, the triplet emitter is a metal complex of the formula M ₂ (L)n. Wherein M ₂ is a metal atom; each occurrence of L may be the same or different, and is an organic ligand which is bonded to the metal atom M by one or more position bonding or coordination; n is a value greater than 1. An integer, preferably 1, 2, 3, 4, 5 or 6. In one embodiment, the metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.

In one embodiment, the metal atom M _{2 is} selected from the group consisting of transition metal elements or lanthanides or actinides. In one embodiment, M is selected from the group consisting of Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu, or Ag. In one embodiment, M is selected from the group consisting of Os, Ir, Ru, Rh, Re, Pd, or Pt.

In one embodiment, the triplet emitter comprises a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites. In one embodiment, the triplet emitter comprises two or three identical or different bidentate or multidentate ligands. Chelating ligands are beneficial for increasing the stability of metal complexes.

Examples of the organic ligand are selected from a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative or a 2-phenylquinoline. A morphine derivative. All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl. The ancillary ligand may be selected from the group consisting of acetone acetate or picric acid.

In a preferred embodiment, the metal complex that can be used as the triplet emitter has the following form:

Wherein M is a metal selected from the group consisting of transition metal elements, lanthanides or actinides.

Ar ¹ is a cyclic group which may be the same or different at each occurrence, and Ar ¹ contains at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group and a metal Coordination linkage; Ar ² is a cyclic group, which may be the same or different at each occurrence, Ar ² contains at least one C atom through which a cyclic group is bonded to the metal; Ar ¹ and Ar ² are covalently The linkages are linked together and may each carry one or more substituent groups, which may also be joined together by a substituent group; L may be the same or different at each occurrence, and L is an auxiliary ligand, preferably a double-sided chelate The ligand, preferably a monoanionic bidentate chelate ligand; m is selected from 1, 2 or 3; n is selected from 0, 1 or 2. In one embodiment, L is a bidentate chelate ligand. In one embodiment, L is a monoanionic bidentate chelate ligand. In one of the embodiments, m is 2 or 3. In one of the embodiments, m is 3. In one of the embodiments, n is 0 or 1. In one of the embodiments, n is zero.

Examples of the application of materials for some triplet emitters can be found in the following patent documents and documents: WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005 /0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099852, WO 2010102709, US 20070087219A1, US 20090061681A1, US 20010053462A1, Baldo, Thompson et al. Nature 403, (2000), 750 - 753, US 20090061681 A1, US 20090061681 A1, Adachi et al. Appl. Phys. Lett. 78 (2001), 1622-1624, J. Kido et al. Appl. Phys. Lett. 65 (1994), 2124, Kido et al .Chem. Lett. 657, 1990, US 2007/0252517 A1, Johnson et al., JACS 105, 1983, 1795, Wrighton, JACS 96, 1974, 998, Ma et al., Synth. Metals 94, 1998, 245, US 6824895, US 7029766, US 6835469, US 6830828, US 20010053462A1, WO 2007095118A1, US 2012004407A1, WO 2012007088A1, WO2012007087A1, WO 2012007086A1, US 2008027220A1, WO 2011157339A1, CN 102282150A, WO 2009118087A1. The entire contents of the above-listed patent documents and documents are hereby incorporated by reference.

Some examples of suitable triplet emitters are listed in the table below.

3. TADF materials

Traditional organic fluorescent materials can only use 25% singlet excitons formed by electrical excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescent material enhances the inter-system traversal due to the strong spin-orbit coupling of the center of the heavy atom, it can effectively utilize the singlet excitons and triplet exciton luminescence formed by electrical excitation, so that the internal quantum efficiency of the device reaches 100%. However, the problems of expensive phosphorescent materials, poor material stability, and severe roll-off of device efficiency limit their application in OLEDs. The thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔEst), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation. The quantum efficiency in the device can reach 100%. At the same time, the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.

TADF materials need to have a small singlet-triplet energy level difference. In one of the embodiments, ΔEst < 0.3 eV. In one of the embodiments, ΔEst < 0.2 eV. In one of the embodiments, ΔEst < 0.1 eV. In one of the embodiments, the TADF material has a relatively small ΔEst. In another embodiment, TADF has better 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., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett ., 101, 2012, 093306, Adachi, et. al. Chem. Commun., 48, 2012, 11392, Adachi, et. al. Nature Photonics, 6, 2012, 253, Adachi, et. al. Nature, 492, 2012,234,Adachi,et.al.J.Am.Chem.Soc,134,2012,14706,Adachi,et.al.Angew.Chem.Int.Ed,51,2012,11311,Adachi,et.al. Chem. Commun., 48, 2012, 9580, Adachi, et. al. Chem. Commun., 48, 2013, 10385, Adachi, et. al. Adv. Mater., 25, 2013, 3319, Adachi, et. .Adv. Mater., 25, 2013, 3707, Adachi, et. al. Chem. Mater., 25, 2013, 3038, Adachi, et. al. Chem. Mater., 25, 2013, 3766, Adachi, et. Al.J. Mater. Chem. C., 1, 2013, 4599, Adachi, et. al. J. Phys. Chem. A., 117, 2013, 5607, hereby incorporated by reference to The entire contents are incorporated herein by reference.

Some examples of suitable TADF luminescent materials are listed in the table below.

In one embodiment, the metal organic complex is used in an evaporated OLED device. At this time, the molecular weight of the metal organic complex is ≤1000 g/mol. In one embodiment, the metal organic complex has a molecular weight of < 900 g/mol. In one embodiment, the metal organic complex has a molecular weight of ≤ 850 g/mol. In one embodiment, the metal organic complex has a molecular weight of < 800 g/mol. In one embodiment, the metal organic complex has a molecular weight of < 700 g/mol.

In one embodiment, the metal organic complex is used in a printed OLED. At this time, the molecular weight of the metal organic complex is ≥700 g/mol. In one of the embodiments, the metal organic complex has a molecular weight of ≥ 800 g/mol. In one embodiment, the metal organic complex has a molecular weight of > 900 g/mol. In one embodiment, the metal organic complex has a molecular weight of > 1000 g/mol. In one embodiment, the metal organic complex has a molecular weight of > 1100 g/mol.

In one embodiment, the above metal organic complex has a solubility in toluene of > 5 mg/ml at 25 °C. In one of the examples, the solubility in toluene is > 8 mg/ml. In one of the examples, the solubility in toluene is > 10 mg/ml.

The mixture of another embodiment includes the above-mentioned polymer, and the various components and contents of the mixture are as described in the mixture of the above embodiment, and will not be described herein.

The composition of an embodiment comprises an organic solvent and the above metal organic complex or polymer or mixture. In this embodiment, the composition is an ink. Thus, the viscosity and surface tension of the ink are important parameters when the composition is used in a printing process. Suitable surface tension parameters for the ink are suitable for the particular substrate and the particular printing method. Further, the present invention provides a film prepared from a solution comprising a metal organic complex or polymer according to the present invention.

In one embodiment, the ink has a surface tension at an operating temperature or at 25 ° C in the range of 19 dyne/cm to 50 dyne/cm. In one of the embodiments, the ink has a surface tension at an operating temperature or at 25 ° C in the range of 22 dyne/cm to 35 dyne/cm. In one of the embodiments, the ink has a surface tension at an operating temperature or at 25 ° C in the range of 25 dyne/cm to 33 dyne/cm.

In one embodiment, the viscosity of the ink at the operating temperature or at 25 ° C is in the range of 1 cps to 100 cps. In one of the embodiments, the viscosity of the ink at the operating temperature or 25 ° C is in the range of 1 cps to 50 cps, in one of the examples, the viscosity of the ink at the operating temperature or 25 ° C. In one of the embodiments, the viscosity of the ink at the operating temperature or at 25 ° C is in the range of 1.5 cps to 20 cps. In one of the embodiments, the viscosity of the ink at the operating temperature or at 25 ° C is in the range of 4.0 cps to 20 cps. This makes the composition more convenient for ink jet printing.

The viscosity can be adjusted by different methods, such as by selection of a suitable solvent and concentration of the functional material in the ink. An ink containing a metal organic complex or a polymer facilitates the adjustment of the printing ink to an appropriate range in accordance with the printing method used. The weight ratio of the organic functional material contained in the composition is from 0.3% to 30% by weight. In one embodiment, the composition The weight ratio of the organic functional material contained in the material is from 0.5% to 20% by weight. In one embodiment, the weight ratio of the organic functional material contained in the composition is from 0.5% to 15% by weight. In one embodiment, the weight ratio of the organic functional material contained in the composition is from 0.5% to 10% by weight. In one embodiment, the weight ratio of the organic functional material contained in the composition is from 1% to 5% by weight.

In an embodiment, the organic solvent comprises a first solvent selected from the group consisting of aromatic and/or heteroaromatic based solvents. Further, the first solvent may be an aliphatic chain/ring-substituted aromatic solvent, or an aromatic ketone solvent, or an aromatic ether solvent.

Examples of the first solvent are, but not limited to, aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene. , 3-isopropylbiphenyl, p-methyl cumene, dipentylbenzene, trimerene, 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, two Benzene, 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 solvent: 1-tetralone, 2-tetralone, 2-(phenyl epoxy) tetralone, 6-(methoxy a tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4 -methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2,6,8-trimethyl-4-indolone, anthrone, 2-nonanone, 3- Anthrone, 5-fluorenone, 2-nonanone, 2,5-hexanedione, phorone, di-n-pentyl ketone; aromatic ether solvent: 3-phenoxytoluene, butoxybenzene, benzyl Butylbenzene, 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-ethyletherether, 1,2,4-trimethoxybenzene, 4-(1-propenyl) )-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-tert-butyl anisole, trans-p-propenyl anisole 1,2-Dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, pentyl ether 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 solvent: octanoic acid Alkyl esters, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamate, alkyl oxalates, alkyl maleates, alkanolactones, alkyl oleates, and the like.

Further, the first solvent may also be selected from aliphatic ketones, for example, 2-nonanone, 3-fluorenone, 5-fluorenone, 2-nonanone, 2,5-hexanedione, 2,6,8 - trimethyl-4-indolone, phorone, di-n-pentyl ketone, etc.; or an aliphatic ether, for example, pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol II Ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether and tetraethylene One or more of the glycerols.

In one embodiment, the organic solvent further includes a second solvent selected from the group consisting of methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, Anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-benzene Oxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl One or more of a sulfoxide, tetrahydronaphthalene, decalin, and anthracene.

In an embodiment, the composition can be a solution or suspension. This is determined based on the compatibility between the organic mixture and the organic solvent.

The use of the above composition as a coating or printing ink in the preparation of an organic electronic device is particularly preferred by a printing or coating preparation method.

Among them, suitable printing or coating techniques include, but are not limited to, inkjet printing, Nozzle Printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion rolls. Printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing or slit-type extrusion coating. Preferred are gravure, inkjet and inkjet printing. The composition may further include a component example, and the cap component is selected from one or more of a surface active compound, a lubricant, a wetting agent, a dispersing agent, a hydrophobic agent, and a binder, thereby being used for adjusting viscosity. , film forming properties, improved adhesion and the like. For more information on printing techniques and their requirements for solutions, such as solvents and concentrations, viscosity, etc., please refer to Helmut Kipphan's "Printing Media Handbook: Techniques and Production Methods" (Handbook of Print Media: Technologies) And Production Methods), ISBN 3-540-67326-1.

In one embodiment, the above metal organic complex or polymer is used in an organic electronic device. The organic electronic device may be selected from an Organic Light-Emitting Diode (OLED), an Organic Photovoltaic (OPV), an Organic Light Emitting Battery (OLEEC), an organic field effect transistor (OFET), and an organic organic device. Luminescent field effect transistor, organic laser, organic spintronic device, organic sensor or Organic Plasmon Emitting Diode. In an embodiment, the organic electronic device is an OLED. Further, the excessive metal complex is used for the light emitting layer of the OLED.

The organic electronic device of an embodiment comprises at least one of the above metal organic complexes or polymers or mixtures. Wherein, the organic electronic device may include a cathode, an anode, and a functional layer between the cathode and the anode, the functional layer comprising the above-mentioned excessive metal complex or the above polymer or the above mixture, or the functional layer is prepared from the above composition. Specifically, the organic electronic device comprises at least a cathode, an anode and a functional layer between the cathode and the anode, the functional layer comprising at least one of the above organic compounds or the above polymer or the above organic mixture, or the functional layer is prepared from the above composition Made. The functional layer is selected from one or more of a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, an electron transport layer, an electron blocking layer, and a light emitting layer.

The organic electronic device may be selected from an Organic Light-Emitting Diode (OLED), an Organic Photovoltaic (OPV), an Organic Light Emitting Battery (OLEEC), an organic field effect transistor (OFET), and an organic organic device. Luminescent field effect transistor, organic laser, organic spintronic device, organic sensor or Organic Plasmon Emitting Diode. In an embodiment, the organic electronic device is an organic electroluminescent device such as an OLED.

In an embodiment, the OLED includes a substrate, an anode, a light-emitting layer, and a cathode that are sequentially stacked. Wherein, the number of layers of the light-emitting layer is at least one layer.

The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent luminescent component, 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 also be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In one embodiment, the substrate is flexible, optionally in a polymeric film or plastic, having a glass transition temperature Tg of 150 ° C or higher. The flexible substrate can be poly(ethylene terephthalate) (PET) or polyethylene glycol (2,6-naphthalene) (PEN). In one of the embodiments, the substrate has a glass transition temperature Tg of 200 ° C or higher. In one of the embodiments, the substrate has a glass transition temperature Tg of 250 ° C or higher. In one of the embodiments, the substrate has a glass transition temperature Tg of 300 ° C or higher.

The anode can include a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a hole injection layer (HIL) or a hole transport layer (HTL) or a light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.5eV. The absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.3 eV. The absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.2 eV. Examples of the anode material include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, and aluminum-doped zinc oxide (AZO). The anode material can also be other materials. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In other embodiments, the anode is patterned. A patterned ITO conductive substrate is commercially available and can be used to prepare an organic electronic device according to the present embodiment.

The cathode can include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer. In one embodiment, the work function of the cathode and the LUMO level or conductance of the illuminant in the luminescent layer or the n-type semiconductor material as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL) The absolute value of the difference in band level is less than 0.5 eV. The work function of the cathode and the difference in LUMO energy level or conduction band energy level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL) in the light-emitting layer The absolute value is less than 0.3 eV. The work function of the cathode and the difference in LUMO energy level or conduction band energy level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL) in the light-emitting layer The absolute value is less than 0.2 eV. All materials which can be used as the cathode of the OLED are possible as the cathode material of the organic electronic device of the present embodiment. 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, and the like. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, and electron beam (e-beam).

The OLED may further 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 above.

In one embodiment, in the light-emitting device according to the invention, the light-emitting layer comprises a metal-organic complex or polymer according to the invention, which can be prepared by vacuum evaporation or solution processing.

In an embodiment, the organic electroluminescent device light-emitting device has an emission wavelength between 300 and 1000 nm. In one of the embodiments, the organic electroluminescent device light-emitting device has an emission wavelength between 350 and 900 nm. In one of the embodiments, the organic electroluminescent device light-emitting device has an emission wavelength of between 400 and 800 nm.

In one embodiment, the above-described organic electronic device is used in an electronic device. The electronic device is selected from a display device, a lighting device, a light source or a sensor. Among them, the organic electronic device may be an organic electroluminescent device.

An electronic device comprising the above organic electronic device.

The present invention will be described with reference to the preferred embodiments thereof, but the present invention is not limited to the embodiments described below. It is to be understood that the scope of the invention is intended to be It is to be understood that the modifications of the various embodiments of the invention are intended to be

1. Metal organic complexes and their energy structures

The energy levels of the metal-organic complexes Au-1, Au-2, Au-3, Au-4 can be obtained by quantum calculations, such as by TD-DFT (time-dependent density functional theory) by Gaussian03W (Gaussian Inc.). The simulation method can be found in WO2011141110. First, use the semi-empirical method "Ground State/Hartree-Fock/Default Spin/LanL2MB" (Charge 0/Spin Singlet) to optimize the molecular geometry. Then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method. Calculated as "TD-SCF/DFT/Default Spin/B3PW91/gen geom=connectivity pseudo=lanl2" (Charge 0/Spin Singlet). The HOMO and LUMO levels are calculated according to the following calibration formula, and S1 and T1 are used directly.

HOMO(eV)=((HOMO(Gaussian)×27.212)-0.9899)/1.1206

LUMO(eV)=((LUMO(Gaussian)×27.212)-2.0041)/1.385

Among them, HOMO(G) and LUMO(G) are direct calculation results of Gaussian 03W, and the unit is Hartree. The results are shown in Table 1.

Table I

2. Synthesis of metal organic complexes

Example 1: Synthesis of complex Au-1

Synthetic Intermediate A:

3-bromobenzaldehyde (16 g, 1 eq) and o-phenylenediamine (10.28 g, 1 eq) were placed in a 500 mL three-necked flask under nitrogen atmosphere, and then acetonitrile (300 mL) and 37% aqueous hydrogen chloride solution were added thereto. (30 mL, 3.5 eq), then 30% aqueous hydrogen peroxide (68 mL, 7 eq) was slowly added dropwise under ice bath (0 ° C) and stirred for 4 hr. It was then mixed with a large amount of water (1000 mL), and the solid was filtered to give a brown solid Intermediate A, yield 90%.

Synthetic Intermediate B:

6-Bromo-2-pyridinecarboxylic acid (17.5 g, 1 eq) and o-phenylenediamine (10.28 g, 1 eq) were placed in a 500 mL three-necked flask under nitrogen atmosphere, and then acetonitrile (300 mL) was added thereto. And a 37% aqueous solution of hydrogen chloride (30 mL, 3.5 eq), and then a 30% aqueous hydrogen peroxide solution (68 mL, 7 eq) was slowly added dropwise under ice bath (0 ° C) and stirred for 4 hours. It was then mixed with a large amount of water (1000 mL), and the solid was filtered to give a brown solid Intermediate B.

Synthetic intermediate C:

Intermediate A (1.50 g, 1 eq), aniline (1.03 g, 2 eq), Pd ₂ (dba) ₃ (0.5 g, 0.1 eq), X-Phos (0.24 g, 0.1 eq) were placed in a 250 mL three-necked flask. Sodium tert-butoxide (5.31 g, 10 eq) was repeatedly vacuumed and filled with nitrogen three times, then toluene (120 mL) was then added and then warmed to 120 ° C and stirred for 4 hours. Then, the solvent was distilled off under reduced pressure, and water (250 mL) and dichloromethane (250 mL) were added to extract, and the organic layer was taken, and concentrated under reduced pressure, and then a solvent mixture of ethyl acetate and petroleum ether in a ratio of 1:5. The most fractions were taken and the fractions were concentrated under reduced pressure to give a brown solid intermediate C, yield 25%.

Synthetic intermediate D:

Intermediate B (1.80 g, 1 eq), intermediate C (1.88 g, 2 eq), Pd ₂ (dba) ₃ (0.6 g, 0.1 eq), X-Phos (0.29 g, 0.1) were placed in a 100 mL three-necked flask. Eq) and sodium tert-butoxide (6.33 g, 10 eq) were repeatedly vacuumed and filled three times with nitrogen, then toluene (60 mL) was then added and then warmed to 120 ° C and stirred for 24 hours. Then, the solvent was distilled off under reduced pressure, and water (250 mL) and dichloromethane (250 mL) were added to extract, and the organic layer was taken, and concentrated under reduced pressure, and then a solvent mixture of ethyl acetate and petroleum ether in a ratio of 1:5. The most fractions were taken and the fractions were concentrated under reduced pressure to give a brown solid intermediate D, yield 20%.

Synthetic complex Au-1:

Intermediate D (0.3 g, 1 eq), KAuCl ₄ .2H ₂ O (0.29 g, 1.1 eq) and potassium carbonate (0.61 g, 10 eq) were placed in a 100 mL three-necked flask under nitrogen atmosphere and then added thereto. Methanol (30 mL) was stirred at room temperature for 12 hours. Then, the solvent was distilled off under reduced pressure, extracted with dichloromethane, and the organic layer was taken, and concentrated under reduced pressure. Then, a mixture of dichloromethane and petroleum ether in a ratio of 1:5 was passed through a silica gel to obtain a yellow component. Concentration under reduced pressure, and recrystallization from an appropriate amount of ethanol to give a yellow-green complex, Au-1, yield 35%.

Example 2: Synthesis Complex Au-2

Synthetic intermediate E:

In a 1000 mL three-necked flask, 1,3-dibromobenzene (15 g, 1 eq), Pd(PPh ₃ ) ₄ (1.46 g, 0.02 eq), and potassium carbonate (35 g, 4 eq) were placed in a nitrogen-filled atmosphere. Then, toluene (200 mL) and water (100 mL) were added as a solvent, and the mixture was heated to 120 ° C, and then a solution of bismuth borate (16 g, 0.8 eq) in toluene (150 mL) was added dropwise thereto, followed by stirring at 120 ° C for 24 hours. . Then, it was mixed with a large amount of water (1000 mL), and the upper organic layer was extracted and concentrated under reduced pressure. Then, a mixture solvent of ethyl acetate and petroleum ether in a ratio of 1:10 was passed through silica gel to obtain the most components, and the fraction was concentrated under reduced pressure. The brown solid intermediate E was obtained in a yield of 88%.

Synthetic intermediate F:

2,6-dibromopyridine (15 g, 1 eq), Pd(PPh ₃ ) ₄ (1.46 g, 0.02 eq) and potassium carbonate (35 g, 4 eq) were placed in a 1000 mL three-necked flask in a nitrogen-filled atmosphere. Then, toluene (200 mL) and water (100 mL) were added as a solvent, and the mixture was heated to 120 ° C, and then a solution of bismuth borate (16 g, 0.8 eq) in toluene (150 mL) was added dropwise thereto, followed by stirring at 120 ° C for 24 hours. . Then, it was mixed with a large amount of water (1000 mL), and the upper organic layer was extracted and concentrated under reduced pressure. Then, a mixture of ethyl acetate and petroleum ether in a ratio of 1:5 was passed through silica gel to obtain the most components, and the fraction was concentrated under reduced pressure. The brown solid intermediate F was obtained in a yield of 69%.

Synthetic intermediate G:

Intermediate E (1.50 g, 1 eq), aniline (1.03 g, 2 eq), Pd ₂ (dba) ₃ (0.5 g, 0.1 eq), X-Phos (0.24 g, 0.1 eq) were placed in a 250 mL three-necked flask. Sodium tert-butoxide (5.31 g, 10 eq) was repeatedly vacuumed and filled with nitrogen three times, then toluene (120 mL) was then added and then warmed to 120 ° C and stirred for 4 hours. Then, the solvent was distilled off under reduced pressure, and water (250 mL) and dichloromethane (250 mL) were added to extract, and the organic layer was taken, and concentrated under reduced pressure, and then a solvent mixture of ethyl acetate and petroleum ether in a ratio of 1:5. The most fractions were taken, and the fraction was concentrated under reduced pressure to give a brown solid intermediate G, yield 22%.

Synthetic intermediate H:

Intermediate F (1.80 g, 1 eq), intermediate G (1.88 g, 2 eq), Pd ₂ (dba) ₃ (0.6 g, 0.1 eq), X-Phos (0.29 g, 0.1) were placed in a 100 mL three-necked flask. Eq) and sodium tert-butoxide (6.33 g, 10 eq) were repeatedly vacuumed and filled three times with nitrogen, then toluene (60 mL) was then added and then warmed to 120 ° C and stirred for 24 hours. Then, the solvent was distilled off under reduced pressure, and water (250 mL) and dichloromethane (250 mL) were added to extract, and the organic layer was taken, and concentrated under reduced pressure, and then a solvent mixture of ethyl acetate and petroleum ether in a ratio of 1:5. The most fractions were taken and the fractions were concentrated under reduced pressure to give a brown solid intermediate H, yield 26%.

Synthetic complex Au-2:

Intermediate H (0.3 g, 1 eq), KAuCl ₄ .2H ₂ O (0.29 g, 1.1 eq) and potassium carbonate (0.61 g, 10 eq) were placed in a 100 mL three-necked flask under nitrogen atmosphere and then added thereto. Methanol (30 mL) was stirred at room temperature for 12 hours. Then, the solvent was distilled off under reduced pressure, extracted with dichloromethane, and the organic layer was taken, and concentrated under reduced pressure. Then, a mixture of dichloromethane and petroleum ether in a ratio of 1:5 was passed through a silica gel to obtain a yellow component. Concentration under reduced pressure, and recrystallization from an appropriate amount of ethanol to give a yellow compound, Au-2, yield 30%.

Example 3: Synthesis complex Au-3

Synthetic Intermediate I:

3-Hydroxybenzaldehyde (10.56 g, 1 eq) and o-phenylenediamine (10.28 g, 1 eq) were placed in a 500 mL three-necked flask under nitrogen atmosphere, and then acetonitrile (300 mL) and 37% hydrogen chloride were added thereto. Aqueous solution (30 mL, 3.5 eq) was then slowly added dropwise with 30% aqueous hydrogen peroxide (68 mL, 7 eq) under ice bath (0 ° C) and stirred for 4 hr. It was then mixed with a large amount of water (1000 mL), and the solid was filtered to give a brown solid Intermediate I.

Synthetic intermediate J:

6-Bromo-2-pyridinecarboxylic acid (17.5 g, 1 eq) and o-phenylenediamine (10.28 g, 1 eq) were placed in a 500 mL three-necked flask under nitrogen atmosphere, and then acetonitrile (300 mL) was added thereto. And a 37% aqueous solution of hydrogen chloride (30 mL, 3.5 eq), and then a 30% aqueous hydrogen peroxide solution (68 mL, 7 eq) was slowly added dropwise under ice bath (0 ° C) and stirred for 4 hours. It was then mixed with a large amount of water (1000 mL), and the solid was filtered to give a brown solid intermediate J, yield 67%.

Synthetic intermediate K:

Intermediate I (5.00 g, 1 eq), intermediate J (7.82 g, 1.2 eq), Cs ₂ CO ₃ (7.75 g, 1 eq) and Cu (0.3 g, 0.2 eq) were placed in a 100 mL three-necked flask. Vacuum was applied and filled three times with nitrogen, then DMF (5 mL) was added, heated to 140 ° C and stirred for 24 hours. Then, water (250 mL) and dichloromethane (250 mL) were added for extraction, and the lower organic solution was taken, and concentrated under reduced pressure, and then the silica gel was mixed with a solvent mixture of ethyl acetate and petroleum ether in a ratio of 1:3 to obtain the most components. The fraction was concentrated under reduced pressure to give a brown solid intermediate K (yield: 34%).

Synthetic complex Au-3:

Intermediate K (0.26 g, 1 eq), KAuCl ₄ .2H ₂ O (0.29 g, 1.1 eq) and potassium carbonate (0.61 g, 10 eq) were placed in a 100 mL three-necked flask in a nitrogen-filled atmosphere. Methanol (30 mL) was added thereto, and the mixture was stirred at room temperature for 12 hours. Then, the solvent was distilled off under reduced pressure, extracted with dichloromethane, and the organic layer was taken, and concentrated under reduced pressure. Then, a mixture of dichloromethane and petroleum ether in a ratio of 1:5 was passed through a silica gel to obtain a yellow component. Concentration under reduced pressure and recrystallization from an appropriate amount of ethanol afforded pale yellow compound Au-3, yield 32%.

Example 4: Synthesis complex Au-4

Synthetic intermediate L:

Place m-bromophenol (10.56 g, 1 eq), 2-barium borate (16 g, 0.8 eq), Pd(PPh ₃ ) ₄ (1.46 g, 0.02 eq) in a 1000 mL three-necked flask in a nitrogen-filled atmosphere. Potassium carbonate (35 g, 4 eq) was then added toluene (400 mL) and water (100 mL) as a solvent and stirred to 120 ° C for 24 hours. Then, it was mixed with a large amount of water (1000 mL), and the upper organic layer was extracted and concentrated under reduced pressure. Then, a mixture solvent of ethyl acetate and petroleum ether in a ratio of 1:10 was passed through silica gel to obtain the most components, and the fraction was concentrated under reduced pressure. The brown solid intermediate L was obtained in a yield of 82%.

Synthetic intermediate M:

2,6-dibromopyridine (15 g, 1 eq), Pd(PPh ₃ ) ₄ (1.46 g, 0.02 eq) and potassium carbonate (35 g, 4 eq) were placed in a 1000 mL three-necked flask in a nitrogen-filled atmosphere. Then, toluene (200 mL) and water (100 mL) were added as a solvent, and the mixture was heated to 120 ° C, and then a solution of bismuth borate (16 g, 0.8 eq) in toluene (150 mL) was added dropwise thereto, followed by stirring at 120 ° C for 24 hours. . Then, it was mixed with a large amount of water (1000 mL), and the upper organic layer was extracted and concentrated under reduced pressure. Then, a mixture of ethyl acetate and petroleum ether in a ratio of 1:5 was passed through silica gel to obtain the most components, and the fraction was concentrated under reduced pressure. The brown solid intermediate M was obtained in a yield of 64%.

Synthetic intermediate N:

Intermediate L (5.00 g, 1 eq), intermediate M (7.82 g, 1.2 eq), Cs ₂ CO ₃ (7.75 g, 1 eq) and Cu (0.3 g, 0.2 eq) were placed in a 100 mL three-necked flask. Vacuum was applied and filled three times with nitrogen, then DMF (5 mL) was added, heated to 140 ° C and stirred for 24 hours. Then, water (250 mL) and dichloromethane (250 mL) were added for extraction, and the lower organic solution was taken, and concentrated under reduced pressure, and then the silica gel was mixed with a solvent mixture of ethyl acetate and petroleum ether in a ratio of 1:3 to obtain the most components. The fraction was concentrated under reduced pressure to give a brown solid intermediate N (yield: 36%).

Synthetic complex Au-4:

Intermediate N (0.26 g, 1 eq), KAuCl ₄ .2H ₂ O (0.29 g, 1.1 eq) and potassium carbonate (0.61 g, 10 eq) were placed in a 100 mL three-necked flask under nitrogen atmosphere. Methanol (30 mL) was added thereto, and the mixture was stirred at room temperature for 12 hours. Then, the solvent was distilled off under reduced pressure, extracted with dichloromethane, and the organic layer was taken, and concentrated under reduced pressure. Then, a mixture of dichloromethane and petroleum ether in a ratio of 1:5 was passed through a silica gel to obtain a yellow component. The organic layer was concentrated under reduced pressure, and then recrystallized from ethyl alcohol to give a pale yellow compound of Au-4.

3. Photophysical properties of the complex

As shown in Fig. 1, it can be seen from the solid PL spectrum of Au-1 that the maximum peak of the emission spectrum of the gold (III) complex of the tetradentate ligand is between 500 and 700 nm, indicating that this type of complex is suitable. Electronic device for yellow light.

4. Preparation and characterization of OLED devices

ITO/NPD (60 nm) / 15% Au-1: mCP (45 nm) / TPBi (35 nm) / LiF (1 nm) / Al (150 nm) / cathode The preparation steps of the OLED device are as follows:

a, cleaning of the conductive glass substrate: when used for the first time, can be washed with a variety of solvents, such as chloroform, ketone, isopropyl alcohol, and then UV ozone plasma treatment;

b, HTL (60 nm), EML (45 nm), ETL (35 nm): hot evaporation in high vacuum (1 × 10 ^-6 mbar, mbar);

c, cathode: LiF / Al (1nm / 150nm) in a high vacuum (1 × 10 ^-6 mbar) in the thermal evaporation;

d. Package: The device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.

The current-voltage luminance (JVL) characteristics of OLED devices are characterized by characterization devices while recording important parameters such as efficiency and external quantum efficiency. The maximum external quantum efficiency of the OLED device Au-1 was 5.4%.

The OLED device structure can be further optimized, such as the combined optimization of HTM, ETM and host materials, which will further improve device performance, especially efficiency, drive voltage and lifetime.

Claims (14)

A metal organic complex characterized in that the structure of the metal organic complex is as shown in the formula (1):

among them, M is a metal atom and M is selected from gold or palladium; L is selected from the group consisting of two bridges; Ar ¹ and Ar ^{2 are} independently selected from an aromatic group having 5 to 20 ring atoms, a heteroaromatic group having 5 to 20 ring atoms, or a non-aromatic ring system having 5 to 20 ring atoms; Ar ¹ And Ar ² independently have a substituent R ¹ or R ² ; Ar ³ and Ar ⁴ independently have an aromatic group having 5 to 20 ring atoms, a heteroaromatic group having 5 to 20 ring atoms, or a non-aromatic ring system having 5 to 20 ring atoms; Ar ³ and Ar ⁴ independently has a substituent R ³ or R ⁴ ; R ¹ , R ² , R ³ and R ^{4 are} independently selected from hydrogen, deuterium, a halogen atom or a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and 1 a linear alkenyl group of -20 carbon atoms, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a heteroaromatic group of 1 to 20 carbon atoms or a non-aromatic ring system of 1 to 20 carbon atoms. The metal organic complex according to claim 1, wherein the Ar ¹ and Ar ^{2 are} independently selected from any of the following groups:

Wherein P represents a bond to any position of Ar ³ or Ar ⁴ ; X ¹ -X ¹⁸ independently contains at least one nitrogen, oxygen, carbon, silicon, boron, sulfur or phosphorus atom; R ⁵ -R ^{7 are} independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. a linear alkenyl group, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms Heteroaromatic group or a non-aromatic ring system having 1-20 carbon atoms; Y is selected from the group consisting of two bridged groups. The metal organic complex according to claim 1 or 2, wherein the Ar ¹ and Ar ^{2 are} independently selected from any of the following groups:

Wherein R ^{8 -} R ^{10 are} independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and having 1 to 20 carbons. a linear alkenyl group of an atom, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, having 1 to 20 A heteroaromatic group of a carbon atom or a non-aromatic ring system having 1 to 20 carbon atoms. The metal organic complex according to any one of claims 1 to 3, wherein the Ar ³ and Ar ^{4 are} independently selected from any of the following groups:

Wherein Q represents bonding to any of the Ar ¹ or Ar ² positions; X ¹⁹ -X ³¹ independently comprise at least one nitrogen, oxygen, carbon, silicon, boron, sulfur or phosphorus atom; R ¹¹ -R ^{13 are} independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. a linear alkenyl group, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms Heteroaromatic groups or non-aromatic ring systems having 1-20 carbon atoms. The metal organic complex according to any one of claims 1 to 4, wherein the Ar ³ and Ar ^{4 are} independently selected from any of the following groups:

Wherein R ^{11 to} R ^{13 are} independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. a linear alkenyl group of an atom, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, having 1 to 20 A heteroaromatic group of a carbon atom or a non-aromatic ring system having 1 to 20 carbon atoms. The metal organic complex according to any one of claims 1 to 5, wherein the L is selected from any of the following groups:

Wherein any of the # 1 and Ar represents a position bonded to ^1; # 2 represents any one of a position of the Ar ² bond; the Z comprising at least one nitrogen, oxygen, carbon, silicon, boron, sulfur, or phosphorus atoms R ¹⁸ -R ^{20 are} independently selected from H, D, a halogen atom, CN, NO ₂ , CF ₃ , B(OR) ₂ , Si(R) ₃ , a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 1 to 20 carbon atoms, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether having 1 to 20 carbon atoms a group having an aromatic group of 1 to 20 carbon atoms, a heteroaromatic group having 1 to 20 carbon atoms or a non-aromatic ring system having 1 to 20 carbon atoms; the R is selected from the group consisting of hydrogen and hydrogen, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms A branched alkenyl group, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a heteroaromatic group having 1 to 20 carbon atoms or having 1 to 20 carbon atoms Non-aromatic ring system. The metal-organic complex according to any one of claims 1 to 6, wherein the structure of the metal organic complex is as shown in the formula (I-1) or (I-2):

^{Wherein, R 21, R 22, R} 23 and R ²⁴ are independently selected from hydrogen, deuterium, a halogen atom, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 1 to 20 carbon atoms, a branched alkenyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms a heteroaromatic group having 1 to 20 carbon atoms or a non-aromatic ring system having 1 to 20 carbon atoms; X ³² -X ³⁷ independently containing at least one nitrogen, oxygen, carbon, silicon, boron, sulfur or Phosphorus atom. The metal organic complex according to claim 7, wherein the metal organic complex is selected from one of the complexes represented by the formula:

A polymer characterized in that at least one repeating unit of the polymer comprises the metal organic complex according to any one of claims 1-8. A mixture, characterized in that the mixture comprises at least one organic functional material and a metal organic complex according to any one of claims 1-8 or a polymer according to claim 9; The functional material is selected from the group consisting of a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, an electron blocking material, a hole blocking material, an illuminant, a host material, or a doping material. A composition comprising an organic solvent and a metal organic complex according to any one of claims 1-8 or a polymer according to claim 9 or as claimed in claim 10. Said mixture. The metal organic complex according to any one of claims 1 to 8 or the polymer according to claim 9 or the mixture according to claim 10 or the composition according to claim 11 in the preparation of an organic electronic device Applications. An organic electronic device comprising the metal organic complex according to any one of claims 1 to 8 or the polymer according to claim 9 or the mixture according to claim 10. The organic electronic device according to claim 13, 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, and an organic Spintronics, organic sensors or organic plasmon emitting diodes.