CN109678907B - Metal platinum (II) complex containing bridged phenyl-pyrazole structural unit - Google Patents

Abstract

The invention provides a metal platinum (II) complex containing a bridged phenyl-carbazole structural unit and application thereof. The metal platinum (II) complex has a structure represented by the general formula (I). The luminescent material provided by the invention regulates and controls the photophysical properties of the tetradentate ring metal platinum (II) complex by regulating the structure of the ligand surrounding the metal center and regulating and controlling the structure of the substituent group on the ligand, and has the advantages of high stability and high efficiency; the method has wide application prospect in various fields such as OLED display and illumination.

Description

Metal platinum (II) complex containing bridged phenyl-pyrazole structural unit

Technical Field

The invention relates to the technical field of organic luminescent materials, in particular to a tetradentate ring metal platinum (II) complex phosphorescence and delayed fluorescence or pure phosphorescence luminescent material containing bridged phenyl-pyrazole structural units and application thereof.

Background

Compounds capable of absorbing and/or emitting light are suitable for use in a variety of optical and electroluminescent devices, including: light absorbing, solar and photosensitive devices, Organic Light Emitting Diodes (OLEDs), light emitting devices, or devices capable of both light absorption and light emission and as markers (markers) for biological applications. Much research has been devoted to the discovery and optimization of organic and organometallic materials for use in optical and electroluminescent devices. In general, research in this field is aimed at achieving a number of goals, including improvements in absorption and emission efficiencies, and improvements in processing capabilities.

Good blue light emitting materials in the organic light emitting materials are rare, the stability of a blue light device is not good enough, and compared with red and green phosphorescent materials, the lowest triplet state energy level of the blue light phosphorescent materials is higher, which means that the stability of the phosphorescent materials in the blue light device is more important.

Typically, a change in chemical structure affects the electronic structure of a compound, thereby affecting its optical properties (e.g., emission and absorption spectra), and thus, changing the chemical structure can cause the compound to have particular emission or absorption characteristics. In addition, the optical properties of the compounds can also be modulated by changing the ligands at the structural center. For example, compounds bearing ligands with electron donating or electron withdrawing substituents often exhibit different optical properties, including different emission and absorption spectra.

Because the phosphorescent multidentate platinum metal complexes can simultaneously utilize singlet excitons and triplet excitons which are electrically excited, 100% of internal quantum efficiency is obtained, and the complexes can be used as alternative luminescent materials of OLEDs. In general, the ligand of the multidentate platinum metal complex includes a luminescent group and an auxiliary group. If a conjugated group is introduced, for example, an aromatic ring substituent or a heteroatom substituent is introduced into a luminescent molecule, the energy levels of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) of the luminescent material can be changed, and at the same time, the energy level gap between the HOMO orbital and the LUMO orbital can be further adjusted, so that the emission spectrum property of the phosphorescent multidentate platinum metal complex can be adjusted, for example, the emission spectrum property can be made wider or narrower, or the emission spectrum property can be made blue-shifted. Thereby meeting the need for improved performance in light emitting and absorbing applications.

Although the literature has many reports on bivalent cyclometalated platinum (II) metal complex phosphorescent materials, the tetradentate cyclometalated platinum (II) complex containing bridged phenyl-pyrazole structural units has not been reported yet.

Disclosure of Invention

The invention aims to provide a tetradentate ring metal platinum (II) complex containing a bridged phenyl-pyrazole structural unit, and the complex can be used as a luminescent material in an OLED device. According to the invention, the benzene ring and the pyrazole ring are linked by the linking group, so that the dihedral angle of phenyl-pyrazole can be effectively reduced to approach zero, the conjugation degree between the phenyl-pyrazole and the pyrazole ring is greatly improved, and the triplet state energy level of cyclometalated platinum (II) complex can be effectively adjusted to be greatly reduced; meanwhile, the strong spin-orbit coupling effect of the platinum metal ions enables the complex to emit blue-shifted delayed fluorescence at room temperature spectrum, so that blue light can be emitted by a material with small triplet state energy level based on the design, and a powerful solution is provided for the development of stable blue light OLED. In addition, the platinum (II) complex also has the advantages of high molecular rigidity and good stability; the metal platinum (II) complex is applied to a light-emitting device, can improve the light-emitting efficiency and the operation time of the device, and has wide application prospect in various fields such as OLED display, illumination and the like.

The technical scheme of the invention is as follows: in a first aspect, embodiments of the present invention provide a metal platinum (II) complex comprising bridged phenyl-pyrazole building blocks, the metal platinum (II) complex having a structure according to formula (I)

（I）

Wherein:

the linking group X is selected from CH₂、CHD、 CD₂、CR¹⁰⁰R¹⁰¹、SiH₂、SiHD、SiD₂、SiR¹⁰²R¹⁰³、GeH₂、Ge HD、GeD₂、GeR¹⁰⁴R¹⁰⁵；

A is selected from O, S, CH₂、CHD、CD₂、CR²⁰⁰R²⁰¹、C=O、SiR²⁰²R²⁰³、GeH₂、GeR²⁰⁴R²⁰⁵、NH、ND、NR²⁰⁶、PH、PD、PR²⁰⁷、R²⁰⁸P=O、AsR²⁰⁹、R²¹⁰As=O、S=O、SO₂、Se、Se=O、SeO₂、BH、BD、BR²¹¹、R²¹²Bi = O, BiH, BiD, or BiR²¹³；

R^a、R^b、R^c、R^d、R^e、R^fAnd R^gEach independently selected from the group consisting of hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxyCarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, silyl, substituted silyl, polymeric group, or a combination thereof; r^a、R^b、R^c、R^d、R^e、R^fAnd R^gThe substitution modes of (A) are respectively and independently represented as mono-substitution, di-substitution, tri-substitution, tetra-substitution or non-substitution, and two adjacent substituents can form a condensed ring;

s represents an integer of 0 to 5, m and n each independently represent an integer of 0 to 4, o represents an integer of 0 to 2, p and r each independently represent an integer of 0 to 3, and q represents an integer of 0 to 1;

the R is¹⁰⁰、R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴、R¹⁰⁵、R²⁰⁰、R²⁰¹、R²⁰²、R²⁰³、R²⁰⁴、R²⁰⁵、R²⁰⁶、R²⁰⁷、R²⁰⁸、R²⁰⁹、R²¹⁰、R²¹¹、R²¹²、R²¹³Each independently selected from aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxy, hydrazino, silyl, substituted silyl, polymeric group, or a combination thereof; wherein two adjacent substituents may form a condensed ring;

ar is¹Is phenyl linked to pyrazolyl, Ar is²Is with Ar¹Linked phenyl, said alpha being Ar¹Dihedral angle with pyrazolyl, said beta is Ar¹And Ar²The dihedral angle of (1).

Optionally, the metal platinum (II) complex has a structure represented by general formulas (II) and (III):

wherein R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰And R¹¹Each independently is hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imine, sulfo, carboxyl, hydrazine, silyl, substituted silyl, a polymeric group, or a combination thereof; adjacent said R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰And R¹¹May be joined to form a fused ring.

Optionally, the metal platinum (II) complex has a structure represented by general formulas (IV) and (V):

wherein R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰And R¹¹Each independently selected from the group consisting of hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, iso-aryl, nitro, cyano, amino, alkoxy, aryl, heteroaryl, and the likeA nitrile group, a heteroaryl group, an alkoxycarbonyl group, an amido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramido group, an imine group, a sulfo group, a carboxyl group, a hydrazino group, a silyl group, a substituted silyl group, a polymeric group, or a combination thereof; adjacent said R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰And R¹¹May be joined to form a fused ring.

Optionally, the R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰And R¹¹Each independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, or octylphenyl.

Optionally, the metal platinum (II) complex has a structure of one of:

。

embodiments of the present invention provide that the above-described metal platinum (II) complexes containing bridged phenyl-pyrazole building blocks have a neutral charge.

Embodiments of the present invention also provide for the use of the above-described metal platinum (II) complexes containing bridged phenyl-pyrazole building blocks in electroluminescent devices.

Furthermore, embodiments of the present invention also provide a device comprising a metal platinum (II) complex comprising a bridged phenyl-pyrazole building block as described above.

Optionally, the device is a full color display, a photovoltaic device, a light emitting display device, an organic light emitting diode, or a phosphorescent organic light emitting diode.

Alternatively, there is provided in an embodiment of the present invention a device comprising at least one cathode, at least one anode and at least one light emitting layer, at least one of said light emitting layers comprising a metal platinum (II) complex comprising a bridged phenyl-pyrazole building block as described above.

The invention has the beneficial effects that: one, Ar of phenyl group through linking group¹Linked with pyrazolyl groups for effective reduction of phenyl Ar¹-a pyrazole dihedral angle α, bringing it towards zero, enhancing the rigidity of the molecule; secondly, by regulating phenyl Ar¹-phenyl Ar²Dihedral angle beta, adjustable phenyl Ar¹-phenyl Ar²The degree of conjugation between the two components, and further the luminescence property of the material is effectively adjusted. If phenyl Ar²The ortho-position of (A) has no non-hydrogen substituent, and the steric hindrance of the ortho-position is small, so that the ortho-position is enabled to be in contact with phenyl Ar¹The conjugation degree is larger, and the triplet state energy level of the cyclometalated platinum (II) complex is reduced; meanwhile, the strong spin-orbit coupling effect of the platinum metal ions also enables the complex to emit blue-shifted delayed fluorescence at room temperature spectrum; if at phenyl Ar²The ortho-position of the (A) is introduced with a non-hydrogen substituent, the steric hindrance of which is increased, so that the (A) and the (B) are reacted with Ar¹The conjugation degree is greatly reduced, the triplet state energy level of the cyclometalated platinum (II) complex is increased, and the cyclometalated platinum (II) complex can be directly used as a blue light phosphorescent material. The inventors have found that Ar is phenyl in the compounds of the invention²Whether the ortho-position of the compound has a non-hydrogen substituent or not can realize blue luminescence, provides a powerful solution for the development of stable blue-light OLEDs, and has wide application prospect in various fields such as OLED display, illumination and the like.

[ description of the drawings ]

FIG. 1 is a room temperature emission spectrum of a metal platinum complex Pt3 of the present invention in a methylene chloride solution and a 77K emission spectrum in 2-methyltetrahydrofuran;

FIG. 2 is a room temperature emission spectrum of a metal platinum complex Pt14 of the present invention in a methylene chloride solution and a 77K emission spectrum in 2-methyltetrahydrofuran;

FIG. 3 is a room temperature emission spectrum of a metal platinum complex Pt31 of the present invention in a methylene chloride solution and a 77K emission spectrum in 2-methyltetrahydrofuran;

FIG. 4 is a graph showing the HOMO-1, HOMO, LUMO and LUMO +1 orbital distributions of a platinum metal complex Pt3 according to the present invention;

FIG. 5 is a graph showing the HOMO-1, HOMO, LUMO and LUMO +1 orbital distributions of a platinum metal complex Pt31 according to the present invention;

FIG. 6 is a graph showing the HOMO-1, HOMO, LUMO and LUMO +1 orbital distributions of a platinum metal complex Pt32 according to the present invention;

FIG. 7 is a graph showing the HOMO-1, HOMO, LUMO and LUMO +1 orbital distributions of a platinum metal complex Pt33 according to the present invention;

FIG. 8 is a normalized luminescence spectrum of the metal platinum complex Pt3 of the present invention and a control.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive.

[ detailed description ] embodiments

The invention is further described with reference to the following figures and embodiments.

Before the present compounds, devices, and/or methods are disclosed and described, it is to be understood that they are not limited to the particular synthetic methods (otherwise specified), or to the particular reagents (otherwise specified), as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing, the exemplary methods and materials are described below.

The term "optional" or "optionally" as used herein means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

Disclosed are components useful in preparing the compositions described herein, as well as the compositions themselves to be used in the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds may not be specifically disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed, and a number of modifications that can be made to a number of molecules comprising the compound are discussed, then various and each combination and permutation of the compound are specifically contemplated and may be made, otherwise specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F, and an example of a combination molecule A-D is disclosed, then even if each is not individually recited, it is contemplated that each individually and collectively contemplated combination of meanings, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F, will be disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, it is contemplated that subgroups A-E, B-F, and C-E are disclosed. These concepts are applicable to all aspects of the invention, including but not limited to the steps of the methods of making and using the compositions. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with a specific embodiment or combination of embodiments of the method.

The linking atom used in the present invention can link two groups, for example, N and C groups. The linking atom can optionally (if valency permits) have other chemical moieties attached. For example, in one aspect, oxygen does not have any other chemical group attached because once bonded to two atoms (e.g., N or C) valences have been satisfied. Conversely, when carbon is a linking atom, two additional chemical moieties can be attached to the carbon atom. Suitable chemical moieties include, but are not limited to, hydrogen, hydroxyl, alkyl, alkoxy, = O, halogen, nitro, amine, amide, thiol, aryl, heteroaryl, cycloalkyl, and heterocyclyl.

The term "cyclic structure" or similar terms as used herein refers to any cyclic chemical structure including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclic carbene.

The term "substituted" as used herein is intended to encompass all permissible substituents of organic compounds. In a broad aspect, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents can be one or more, identical or different for suitable organic compounds. For the purposes of the present invention, a heteroatom (e.g. nitrogen) can have a hydrogen substituent and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatom. The present disclosure is not intended to be limited in any way by the permissible substituents of organic compounds. Likewise, the term "substituted" or "substituted with" includes the implicit proviso that such substitution is consistent with the atom being substituted and the allowed valence of the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformation (e.g., by rearrangement, cyclization, elimination, etc.)). It is also contemplated that, in certain aspects, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted), unless explicitly stated to the contrary.

In defining the terms, "R¹”、“R²”、“R³"and" R⁴"used as a general symbol in the present invention denotes various specific substituents. These symbols can be any substituent, are not limited to those disclosed herein, and when they are defined as certain substituents in one instance, they can be defined as some other substituents in other instances.

The term "alkyl" as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, half-yl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may be substituted with one or more groups including, but not limited to, optionally substituted alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, silyl, Sulfo-OXO (Sulfo-OXO), or thiol as described herein. A "lower alkyl" group is an alkyl group containing 1 to 6 (e.g., 1 to 4) carbon atoms.

Throughout the specification, "alkyl" is generally used to refer to both unsubstituted alkyl and substituted alkyl; however, substituted alkyl groups are also specifically mentioned in the present invention by identifying specific substituents on the alkyl group. For example, the term "halogenated alkyl" or "haloalkyl" specifically refers to an alkyl substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine). The term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more amino groups, as described below, and the like. When "alkyl" is used in one instance and a specific term such as "alkyl alcohol" is used in another instance, it is not meant to imply that the term "alkyl" does not refer to the specific term such as "alkyl alcohol" or the like at the same time.

This practice is also applicable to the other groups described in the present invention. That is, when a term such as "cycloalkyl" refers to both unsubstituted and substituted cycloalkyl moieties, the substituted moiety may be otherwise specifically identified in the present invention; for example, a specifically substituted cycloalkyl group can be referred to as, for example, "alkylcycloalkyl". Similarly, a substituted alkoxy group may be specifically referred to as, for example, "halogenated alkoxy", and a specific substituted alkenyl group may be, for example, "enol" and the like. Likewise, practice of using general terms such as "cycloalkyl" and specific terms such as "alkylcycloalkyl" is not intended to imply that the general terms do not also encompass the specific terms.

The term "cycloalkyl" as used herein is a non-aromatic carbon-based ring made up of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, and the like. The term "heterocycloalkyl" is a class of cycloalkyl groups as defined above and is included within the meaning of the term "cycloalkyl" in which at least one ring carbon atom is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl and heterocycloalkyl groups can be substituted or unsubstituted. The cycloalkyl and heterocycloalkyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, silyl, sulfo-oxo, or thiol groups as described herein.

The term "polyalkylene group" as used herein refers to a group containing two or more CH₂Groups and other moieties that are the same are attached. "polyolefin group" can be represented by- (CH)₂)_a-, wherein "a" is an integer of 2 to 500.

The terms "alkoxy" and "alkoxy group," as used herein, refer to an alkyl or cycloalkyl group bonded through an ether linkage; that is, "alkoxy" may be defined as-OR¹Wherein R is¹Is alkyl or cycloalkyl as defined above. "alkoxy" also includes polymers of the alkoxy groups just described; that is, the alkoxy group may be a polyether such as-OR¹-OR²OR-OR¹- (OR²)_a-OR³Wherein "a" is an integer of 1 to 200, and R¹、R²And R³Each independently is an alkyl group, a cycloalkyl group, or a combination thereof.

The term "alkenyl" as used herein is a hydrocarbon group of 2 to 24 carbon atoms, the structural formula of which contains at least one carbon-carbon double bond. Asymmetric structures such as (R)¹R²)C=C(R³R⁴) Intended to include both the E and Z isomers. This is presumed to be in the structural formula of the present invention, wherein asymmetry existsAn alkene, or it may be explicitly represented by the bond symbol C = C. The alkenyl group may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol as described herein.

The term "cycloalkenyl" as used herein is a non-aromatic carbon-based ring, consisting of at least 3 carbon atoms and containing at least one carbon-carbon double bond, i.e., C = C. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, norbornenyl, and the like. The term "heterocycloalkenyl" is a type of cycloalkenyl group as defined above, and is included within the meaning of the term "cycloalkenyl", where at least one carbon atom of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkenyl and heterocycloalkenyl groups can be substituted or unsubstituted. The cycloalkenyl and heterocycloalkenyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol groups as described herein.

The term "alkynyl" as used herein is a hydrocarbon group having 2 to 24 carbon atoms and having a structural formula containing at least one carbon-carbon triple bond. Alkynyl groups can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol groups as described herein.

The term "cycloalkynyl" as used herein is a non-aromatic, carbon-based ring containing at least seven carbon atoms and containing at least one carbon-carbon triple bond. Examples of cycloalkynyl include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like. The term "heterocycloalkynyl" is a type of cycloalkenyl group as defined above and is included within the meaning of the term "cycloalkynyl" wherein at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkynyl and heterocycloalkynyl can be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol as described herein.

The term "aryl" as used herein is a group containing any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term "aryl" also includes "heteroaryl," which is defined as a group containing an aromatic group having at least one heteroatom incorporated into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term "non-heteroaryl" (which is also included in the term "aryl") defines a group that contains an aromatic group, which does not contain heteroatoms. The aryl group may be substituted or unsubstituted. The aryl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde groups, amino, carboxylic acid groups, ester groups, ether groups, halogens, hydroxyl, ketone groups, azido, nitro, silyl, thio-oxo groups, or mercapto groups as described herein. The term "biaryl" is a specific type of aryl group and is included in the definition of "aryl". Biaryl refers to two aryl groups joined together via a bridged ring structure, as in naphthalene, or two aryl groups connected via one or more carbon-carbon bonds, as in biphenyl.

The term "aldehyde" as used herein is represented by the formula-C (O) H. Throughout the specification, "C (O)" is a shorthand form of carbonyl (i.e., C = O).

The term "amine" or "amino" as used herein is defined by the formula-NR¹R²Is represented by the formula (I) in which R¹And R²Can be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl.

The term "alkylamino" as used herein is represented by the formula-NH (-alkyl), wherein alkyl is as described herein. Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, (sec-butyl) amino, (tert-butyl) amino, pentylamino, isopentylamino, (tert-pentyl) amino, hexylamino, and the like.

The term "dialkylamino" as used herein is defined by the formula-N (alkyl)₂Wherein alkyl is as described herein. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di (sec-butyl) amino, di (tert-butyl) amino, dipentylamino, diisopentylamino, di (tert-pentyl) amino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino, and the like.

The term "carboxylic acid" as used herein is represented by the formula-C (O) OH.

The term "ester" as used herein is defined by the formula-OC (O) R¹OR-C (O) OR¹Wherein R1 may be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "polyester" as used herein is represented by the formula- (R)¹O(O)C-R²-C(O)O)_a-or- (R)¹O(O)C-R²-OC(O))_a-represents wherein R¹And R²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and "a" is an integer from 1 to 500. The term "polyester" is used to describe a polyester prepared by having at least two carboxylic acidsA group resulting from a reaction between a compound of the group and a compound having at least two hydroxyl groups.

The term "ether" as used herein is defined by the formula R¹OR²Is represented by the formula (I) in which R¹And R²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "polyether" as used herein is of the formula- (R)¹O-R²O)_a-represents wherein R¹And R²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and "a" is an integer from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutylene oxide.

The term "halogen" as used herein refers to the halogens fluorine, chlorine, bromine, and iodine.

The term "heterocyclyl" as used herein refers to monocyclic and polycyclic non-aromatic ring systems, and "heteroaryl" as used herein refers to monocyclic and polycyclic aromatic ring systems: wherein at least one of the ring members is not carbon. The term includes azetidinyl, dioxanyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl including 1, 2, 3-oxadiazolyl, 1, 2, 5-oxadiazolyl and 1, 3, 4-oxadiazolyl, piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, tetrahydrofuryl, tetrahydropyranyl, tetrazinyl including 1, 2, 4, 5-tetrazinyl, tetrazolyl including 1, 2, 3, 4-tetrazolyl and 1, 2, 4, 5-tetrazolyl, thiadiazolyl including 1, 2, 3-thiadiazolyl, 1, 2, 5-thiadiazolyl and 1, 3, 4-thiadiazolyl, thiazolyl, thienyl, thiadiazolyl including 1, 3, 5-triazinyl and 1, triazinyl groups of 2, 4-triazinyl groups, triazolyl groups including 1, 2, 3-triazolyl groups and 1, 3, 4-triazolyl groups, and the like.

The term "hydroxy" as used herein is represented by the formula-OH.

The term "ketone" as used herein is defined by the formula R¹C(O)R²Is represented by the formula (I) in which R¹And R²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

The term "azido" as used herein is of the formula-N₃And (4) showing.

The term "nitro" as used herein is of the formula-NO₂And (4) showing.

The term "nitrile" as used herein is represented by the formula-CN.

The term "silyl" as used herein, is defined by the formula-SiR¹R²R³Is represented by the formula (I) in which R¹、R²And R³And may independently be hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

The term "thio-oxo" as used herein is defined by the formula-S (O) R¹、-S(O)²R¹、 -OS(O)²R¹or-OS (O)²OR¹Is represented by the formula (I) in which R¹May be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. Throughout the specification, "S (O)" is a shorthand form of S = O. The term "sulfonyl", as used herein, refers to a compound of the formula-S (O)²R¹A thio-oxo group of the formula, wherein R¹Can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl. The term "sulfone" as used herein is defined by the formula R¹S(O)₂R²Is represented by the formula (I) in which R¹And R²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "sulfoxide" as used herein is defined by the formula R¹S(O)R²Is represented by the formula (I) in which R¹And R²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

The term "mercapto" as used herein is represented by the formula-SH

"R" used in the present invention¹”、“R²”、“R³”、“Rⁿ"(wherein n is an integer) may independently have one or more of the groups listed above. For example, if R¹Being a straight chain alkyl, then one hydrogen atom of the alkyl group may be optionally substituted with hydroxyl, alkoxy, alkyl, halogen, and the like. Depending on the group selected, the first group may be incorporated within the second group, or alternatively, the first group may be pendent, i.e., attached, to the second group. For example, for the phrase "alkyl group comprising an amino group," the amino group can be incorporated within the backbone of the alkyl group. Alternatively, the amino group may be attached to the backbone of the alkyl group. The nature of the selected group will determine whether the first group is intercalated or attached to the second group.

The compounds of the present invention may contain "optionally substituted" moieties. Generally, the term "substituted" (whether or not the term "optionally" is present above) means that one or more hydrogens of the indicated moiety are replaced with a suitable substituent. Unless otherwise specified, an "optionally substituted" group may have suitable substituents at each substitutable position of the group, and when more than one position may be substituted with more than one substituent selected from a specified group in any given structure, the substituents at each position may be the same or different. The combinations of substituents contemplated by the present invention are preferably those that form stable or chemically feasible compounds. In certain aspects, it is also contemplated that each substituent may be further optionally substituted (i.e., further substituted or unsubstituted), unless clearly indicated to the contrary.

The structure of the compound can be represented by the following formula:

it is understood to be equivalent to the following formula:

wherein n is throughOften an integer. Namely, RⁿIs understood to mean five individual substituents R^a(1)、R^a(2)、R^a(3)、R^a(4)、R^{a (5)}. By "individual substituents" is meant that each R substituent can be independently defined. For example, if in one instance R^a(m)Is halogen, then in this case R^a(n)Not necessarily halogen.

R is referred to several times in the chemical structures and parts disclosed and described in this specification¹、R²、R³、R⁴、R⁵、R⁶And the like. In the specification, R¹、R²、R³、R⁴、R⁵、R⁶Etc. are each applicable to the citation of R¹、R²、R³、R⁴、R⁵、R⁶Etc., unless otherwise specified.

Optoelectronic devices using organic materials are becoming more and more stringent for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, and therefore organic photovoltaic devices have the potential for cost advantages of inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on flexible substrates. Examples of organic optoelectronic devices include Organic Light Emitting Devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials may have performance advantages over conventional materials. For example, the wavelength at which the organic light-emitting layer emits light can generally be tuned with appropriate dopants.

The excitons decay from the singlet excited state to the ground state to generate instant luminescence, which is fluorescence. If excitons decay from the triplet excited state to the ground state to generate light emission, it is phosphorescence. Phosphorescent metal complexes (e.g., platinum complexes) have shown their potential to utilize both singlet and triplet excitons, achieving 100% internal quantum efficiency, due to the strong spin-orbit coupling of heavy metal atoms between singlet and triplet excited states, effectively enhancing intersystem crossing (ISC). Accordingly, phosphorescent metal complexes are a good choice of dopants in the emissive layer of Organic Light Emitting Devices (OLEDs) and have gained great attention in both academic and industrial fields. Over the last decade, much effort has been made to bring profitable commercialization of this technology, for example, OLEDs have been used for advanced displays for smart phones, televisions and digital cameras.

However, blue electroluminescent devices remain the most challenging area in the art to date, and stability of blue devices is a big problem. The choice of host material has proven to be very important for the stability of blue devices. However, the triplet excited state (T1) lowest energy of the blue light emitting material is very high, which means that the triplet excited state (T1) lowest energy of the host material of the blue device should be higher. This results in increased difficulty in developing the host material for blue devices.

The metal complexes of the present invention can be tailored or tuned to specific applications where specific emission or absorption characteristics are desired. The optical properties of the disclosed metal complexes can be tuned by changing the structure of the ligands surrounding the metal center or by changing the structure of the fluorescent luminophores on the ligands. For example, metal complexes or electron-withdrawing substituents of ligands having electron-donating substituents may generally exhibit different optical properties in the emission and absorption spectra. The color of the metal complex can be adjusted by modifying the fluorescent emitter and the conjugated group on the ligand.

The emission of the complexes of the invention can be modulated, for example, by changing the ligand or fluorescent emitter structure, for example from ultraviolet to near infrared. Fluorescent emitters are a group of atoms in an organic molecule that can absorb energy to produce a singlet excited state, which rapidly decays to produce instant light emission. In one aspect, the complexes of the invention can provide emission in a large portion of the visible spectrum. In a specific example, the complex of the present invention can emit light in the wavelength band of visible light or near infrared light. On the other hand, the complexes of the invention have improved stability and efficiency relative to conventional emissive complexes. In addition, the complexes of the invention may be used as luminescent labels, for example, for biological applications, anticancer agents, emitters in Organic Light Emitting Diodes (OLEDs), or combinations thereof. In another aspect, the complexes of the present invention can be used in light emitting devices, such as Compact Fluorescent Lamps (CFLs), Light Emitting Diodes (LEDs), incandescent lamps, and combinations thereof.

Disclosed herein are platinum-containing compounds or complex complexes. The terms compound or complex are used interchangeably herein. In addition, the compounds disclosed herein have a neutral charge.

The compounds disclosed herein may exhibit desirable properties and have emission and/or absorption spectra that can be tailored by selection of appropriate ligands. In another aspect, the invention can exclude any one or more of the compounds, structures, or portions thereof specifically recited herein.

The compounds disclosed herein are suitable for use in a wide variety of optical and electro-optical devices, including but not limited to light absorbing devices, such as solar and photosensitive devices, Organic Light Emitting Diodes (OLEDs), light emitting devices or devices capable of compatible light absorption and emission and as labels for biological applications.

As mentioned above, the disclosed compounds are platinum complexes. At the same time, the compounds disclosed herein can be used as host materials for OLED applications, such as full color displays.

The compounds disclosed herein are useful in a variety of applications. As a light-emitting material, the compound is useful for organic light-emitting diodes (OLEDs), light-emitting devices and displays, and other light-emitting devices.

In addition, the compounds of the present invention are used in light emitting devices (e.g., OLEDs) to improve the luminous efficiency and the operation time of the devices, relative to conventional materials.

The compounds of the present invention may be prepared using a variety of methods, including but not limited to those described in the examples provided herein.

The compounds disclosed herein may be delayed fluorescence and/or phosphorescence emitters. In one aspect, the compounds disclosed herein can be delayed fluorescence emitters. In one aspect, the compounds disclosed herein can be phosphorescent emitters. In another aspect, the compounds disclosed herein can be delayed fluorescence emitters and phosphorescence emitters.

The invention relates to an organic luminescent material, which comprises a tetradentate metal platinum complex of benzene ring-pyrazole and derivatives thereof, and the tetradentate metal platinum complex can be used as a phosphorescent luminescent material in an OLED device and is used for improving the efficiency and the service life of the device.

Disclosed in embodiments of the present invention is a tetradentate ring platinum (II) complex with bridged phenyl-pyrazole building blocks, the tetravalent metal platinum (II) complex having a structure represented by general formula (I):

（I）

wherein:

the linking group X is selected from CH₂、CHD、 CD₂、CR¹⁰⁰R¹⁰¹、SiH₂、SiHD、SiD₂、SiR¹⁰²R¹⁰³、GeH₂、Ge HD、GeD₂、GeR¹⁰⁴R¹⁰⁵；

A is selected from O, S, CH₂、CHD、CD₂、CR²⁰⁰R²⁰¹、C=O、SiR²⁰²R²⁰³、GeH₂、GeR²⁰⁴R²⁰⁵、NH、ND、NR²⁰⁶、PH、PD、PR²⁰⁷、R²⁰⁸P=O、AsR²⁰⁹、R²¹⁰As=O、S=O、SO₂、Se、Se=O、SeO₂、BH、BD、BR²¹¹、R²¹²Bi = O, BiH, BiD, or BiR²¹³；

R^a、R^b、R^c、R^d、R^e、R^fAnd R^gEach independently selected from the group consisting of hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoylAcyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramidyl, imino, sulfo, carboxyl, hydrazino, silyl, substituted silyl, polymeric group, or combinations thereof; r^a、R^b、R^c、R^d、R^e、R^fAnd R^gThe substitution modes of (A) are respectively and independently represented as mono-substitution, di-substitution, tri-substitution, tetra-substitution or non-substitution, and two adjacent substituents can form a condensed ring;

s represents an integer of 0 to 5, m and n each independently represent an integer of 0 to 4, o represents an integer of 0 to 2, p and r each independently represent an integer of 0 to 3, and q represents an integer of 0 to 1;

the R is¹⁰⁰、R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴、R¹⁰⁵、R²⁰⁰、R²⁰¹、R²⁰²、R²⁰³、R²⁰⁴、R²⁰⁵、R²⁰⁶、R²⁰⁷、R²⁰⁸、R²⁰⁹、R²¹⁰、R²¹¹、R²¹²、R²¹³Each independently selected from aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxy, hydrazino, silyl, substituted silyl, polymeric group, or a combination thereof; wherein two adjacent substituents may form a condensed ring;

ar is¹Is phenyl linked to pyrazolyl, Ar is²Is with Ar¹Linked phenyl, said alpha being Ar¹Dihedral angle with pyrazolyl, said beta is Ar¹And Ar²The dihedral angle of (1).

Optionally, the metal platinum (II) complex has a structure represented by general formulas (II) and (III):

wherein R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰And R¹¹Each independently is hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imine, sulfo, carboxyl, hydrazine, silyl, substituted silyl, a polymeric group, or a combination thereof; adjacent said R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰And R¹¹May be joined to form a fused ring.

Optionally, the metal platinum (II) complex has a structure represented by general formulas (IV) and (V):

wherein R in the general formulae (IV) and (V)¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰And R¹¹Each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, or octylphenyl.

Embodiments of the present invention provide the above tetradentate cyclometalated platinum (II) complexes containing bridged phenyl-pyrazole building blocks having neutral charge.

Embodiments of the present invention also provide the use of the above tetradentate ring metal platinum (II) complexes containing bridged phenyl-pyrazole building blocks in electroluminescent devices.

In addition, embodiments of the present invention also provide a device comprising a tetradentate cyclometallated platinum (II) complex comprising a bridged phenyl-pyrazole building block, as described above.

Optionally, the device is a full color display.

Optionally, the device is a photovoltaic device.

Optionally, the device is a light emitting display device.

Optionally, the device is an organic light emitting diode.

Optionally, the device is a purely phosphorescent or phosphorescent and delayed fluorescence organic light emitting diode.

Alternatively, the tetradentate ring metal platinum (II) complex containing bridged phenyl-pyrazole building blocks is selected to have 100% internal quantum efficiency in the device environment.

Alternatively, there is provided in an embodiment of the invention a device comprising at least one cathode, at least one anode and at least one light emitting layer, at least one of the light emitting layers comprising a tetradentate cyclometalated platinum (II) complex comprising a bridged phenyl-pyrazole building block as described above.

1) X group

Wherein X may be selected from CH₂, CHD, CD₂, CR¹⁰⁰R¹⁰¹, SiH₂, SiHD, SiD₂, SiR¹⁰²R¹⁰³, GeH₂, Ge HD, GeD₂Or GeR¹⁰⁴R¹⁰⁵Selecting; the R is¹⁰⁰、R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴、R¹⁰⁵Each independently represents aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or di-basicAlkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, silyl, substituted silyl, polymeric groups, or combinations thereof;

in another aspect, X is C (CH)₃)₂；

In another aspect, X is C: ( ⁿ Bu)₂；

In another aspect, X is CH₂；

In another aspect, X is CR¹⁰⁰R¹⁰¹；

In another aspect, X is Si (CH)₃)₂；

In another aspect, X is Si: ( ⁿ Bu)₂；

In another aspect, X is SiH₂；

In another aspect, X is SiPh₂；

In another aspect, X is SiR¹⁰⁰R¹⁰¹。

2) Group A

Wherein A may be O, S, CH₂, CHD, CD₂, CR²⁰⁰R²⁰¹, C=O, SiR²⁰²R²⁰³, GeH₂, GeR²⁰⁴R²⁰⁵, NH, ND, NR²⁰⁶, PH, PD, PR²⁰⁷, R²⁰⁸P=O, AsR²⁰⁹, R²¹⁰As=O, S=O, SO₂, Se, Se=O, SeO₂, BH, BD, BR²¹¹, R²¹²Bi = O, BiH, BiD, or BiR²¹³(ii) a The R is²⁰⁰、R²⁰¹、R²⁰²、R²⁰³、R²⁰⁴、R²⁰⁵、R²⁰⁶、R²⁰⁷、R²⁰⁸、R²⁰⁹、R²¹⁰、R²¹¹、R²¹²、R²¹³Each independently represents aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, haloA hydroxy group, a mercapto group, a nitro group, a cyano group, an amino group, a mono-or dialkylamino group, a mono-or diarylamino group, an alkoxy group, an aryloxy group, a haloalkyl group, an ester group, a nitrile group, an isonitrile group, a heteroaryl group, an alkoxycarbonyl group, an amido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramido group, an imino group, a sulfo group, a carboxy group, a hydrazine group, a silyl group, a substituted silyl group, a polymeric group, or a combination thereof;

in another aspect, A is O;

in another aspect, A is S;

in another aspect, A is CR²⁰⁰R²⁰¹；

In another aspect, A is NR²⁰⁶；

In another aspect, A is R²⁰⁸P=O；

In another aspect, A is PR²⁰⁷；

In another aspect, A is BR²¹¹；

Further, A is SiR²⁰²R²⁰³。

3) R group

Wherein R is^a Present, on the other hand R^aIs absent.

In one aspect, R^aIs monosubstituted, on the other hand, R^aIs disubstituted; in another aspect, R^aIs a trisubstituted radical; further, R^aIs tetra-substituted;

while R is^aSelected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.

Wherein R is^bPresent, on the other hand R^bIs absent.

In one aspect, R^bIs monosubstituted, on the other hand, R^bIs disubstituted; in another aspect, R^bIs a trisubstituted radical; further, R^bIs tetra-substituted;

while R is^bSelected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.

Wherein R is^cPresent, on the other hand R^cIs absent.

In one aspect, R^cIs monosubstituted, on the other hand, R^cIs disubstituted; in another aspect, R^cIs a trisubstituted radical; further, R^cIs tetra-substituted;

while R is^cSelected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.

Wherein R is^dPresent, on the other hand R^dIs absent.

In one aspect, R^dIs monosubstituted, on the other hand, R^dIs disubstituted;

while R is^dSelected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.

Wherein R is^ePresent, on the other hand R^eIs absent.

In one aspect, R^eIs monosubstituted, on the other hand, R^eIs disubstituted;

while R is^eSelected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.

Wherein R is^fPresent, on the other hand R^fIs absent.

In one aspect, R^fIs monosubstituted, on the other hand, R^fIs disubstituted;

while R is^fFrom hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxyCarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or combinations thereof.

Wherein R is^gPresent, on the other hand R^gIs absent.

In one aspect, R^gIs monosubstituted, on the other hand, R^gIs disubstituted;

while R is^gSelected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.

Wherein R is¹Present, on the other hand R¹Is absent.

In one aspect, R¹Is monosubstituted, on the other hand, R¹Is disubstituted;

while R is¹Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.

Wherein R is²Present, on the other hand R²Is absent.

In one aspect, R²Is monosubstituted, on the other hand, R²Is disubstituted;

while R is²Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.

Wherein R is³Present, on the other hand R³Is absent.

In one aspect, R³Is monosubstituted, on the other hand, R³Is disubstituted;

while R is³Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.

Wherein R is⁴Present, on the other hand R⁴Is absent.

In one aspect, R⁴Is monosubstituted, on the other hand, R⁴Is disubstituted;

while R is⁴From hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or di-basicAlkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric groups, or combinations thereof.

Wherein R is⁵Present, on the other hand R⁵Is absent.

In one aspect, R⁵Is monosubstituted, on the other hand, R⁵Is disubstituted;

while R is⁵Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.

Wherein R is⁶Present, on the other hand R⁶Is absent.

In one aspect, R⁶Is monosubstituted, on the other hand, R⁶Is disubstituted;

while R is⁶From hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, urea, phosphoramido, imine, sulfo, carboxy, hydrazine, substituted silylA polymeric group, or a combination thereof.

Wherein R is⁷Present, on the other hand R⁷Is absent.

In one aspect, R⁷Is monosubstituted, on the other hand, R⁷Is disubstituted;

while R is⁷Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.

Wherein R is⁸Present, on the other hand R⁸Is absent.

In one aspect, R⁸Is monosubstituted, on the other hand, R⁸Is disubstituted;

while R is⁸Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.

Wherein R is⁹Present, on the other hand R⁹Is absent.

In one aspect, R⁹Is monosubstituted, on the other hand, R⁹Is disubstituted;

while R is⁹From hydrogen, deuterium, aryl, cycloalkyl,Cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxy, hydrazino, substituted silyl, polymeric group, or a combination thereof.

Wherein R is¹⁰Present, on the other hand R¹⁰Is absent.

In one aspect, R¹⁰Is monosubstituted, on the other hand, R¹⁰Is disubstituted;

while R is¹⁰Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.

Wherein R is¹¹Present, on the other hand R¹¹Is absent.

In one aspect, R¹¹Is monosubstituted, on the other hand, R¹¹Is disubstituted;

while R is¹¹From hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoylAcyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramidyl, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or combinations thereof.

Exemplary Compounds

In one aspect, any tetradentate cyclometalated platinum (II) complex containing a bridged phenyl-pyrazole building block reported for the present invention may comprise one or more of the following structures. In addition, the metal platinum (II) complex may also include other structures or moieties not specifically enumerated herein, and the scope of the present invention is not limited to the structures and moieties enumerated in this patent.

In embodiments of the present invention, cyclometalated platinum (IV) complexes containing tetradentate ligands are provided having neutral charges.

In embodiments of the present invention, there is also provided the use of cyclometalated platinum (IV) complexes comprising tetradentate ligands in electroluminescent devices. Also disclosed in embodiments of the invention are devices, including full color displays, photovoltaic devices, light emitting display devices, organic light emitting diodes, phosphorescent organic light emitting diodes, and the like, comprising one or more of the compounds disclosed herein. In a device environment, the tetradentate ring metal platinum (II) complex containing bridged phenyl-pyrazole building blocks has 100% internal quantum efficiency.

The disclosed compounds are suitable for use in a variety of optical and electro-optical devices, including but not limited to light absorbing devices such as solar and light sensitive devices, Organic Light Emitting Diodes (OLEDs), light emitting devices or devices having both light absorbing and light emitting capabilities, and as labels for biological applications.

The compounds provided by embodiments of the present invention may be used in a light emitting device, such as an OLED, comprising at least one cathode, at least one anode and at least one light emitting layer, at least one of which comprises the above-described phenylpyrazole-based tetradentate cyclometalated platinum complex. Specifically, the light emitting device may include an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode, which are sequentially deposited. The hole transport layer, the luminescent layer and the electron transport layer are all organic layers, and the anode and the cathode are electrically connected.

Synthetic examples

The following examples of compound syntheses, compositions, articles, devices, or processes are intended to provide a general approach to the art, and are not intended to limit the scope of the patent. Unless otherwise indicated, the weighing is carried out separately, at temperature^oC, or normal temperature, and the pressure is near normal pressure.

The following examples provide methods for the preparation of the novel compounds, but the preparation of such compounds is not limited to this method. In this area of expertise, the compounds protected in this patent can be prepared by the methods listed below or by other methods, since they are easy to modify. The following examples are given by way of example only and are not intended to limit the scope of the patent. The temperature, catalyst, concentration, reactants, and course of reaction can all be varied to select different conditions for the preparation of the compound for different reactants.

¹H NMR（500 MHz）、¹³C NMR (126 MHz) spectra at ANANCE III (50)Measuring on a 0M) type nuclear magnetic resonance spectrometer; unless otherwise specified, nuclear magnetism is induced by DMSO-d ₆ Or CDCl containing 0.1% TMS₃As a solvent, wherein¹H NMR spectrum if CDCl₃As solvent, TMS (δ = 0.00 ppm) was used as internal standard; by DMSO-d ₆ As solvent, TMS (δ = 0.00 ppm) or residual DMSO peak (δ = 2.50 ppm) or residual water peak (δ = 3.33 ppm) was used as internal standard.¹³In the C NMR spectrum, as CDCl₃(delta = 77.00 ppm) or DMSO-d ₆ (δ = 39.52 ppm) as an internal standard. Measuring on an HPLC-MS Agilent 6210 TOF LC/MS type mass spectrometer; HRMS spectra were determined on an Agilent 6210 TOF LC/MS liquid chromatography-time of flight mass spectrometer.¹H NMR spectrum data: s = singlelet, single peak; d = doublet, doublet; t = triplet, triplet; q = quartz, quartet; p = quintet, quintet; m = multiplex, multiplet; br = broad, broad peak.

Synthetic route

The general synthetic method is as follows:

wherein, when the linking group A in the ligand is O, it can be synthesized according to the following route:

or is or

。

Wherein, when the linking group a in the ligand is NR, it can be synthesized by the following route:

or is or

。

Wherein, the B-Br, B-OH and B-NR used in the above route can be synthesized according to the following route:

。

on the other hand, the A-II-OH fragment for A-OH in formula (II) can be synthesized by the following route:

，

。

on the other hand, the A-IV-OH fragment for A-OH in formula (IV) can be synthesized by the following route:

，

。

in addition, if the pyrazole unit in the above structure is replaced by other heterocyclic ring, the synthesis of the tetravalent platinum complex can also be carried out with reference to the above route.

Example 1: the platinum complex Pt3 can be synthesized by the following route:

synthesis of intermediate 1: to a 100 mL dry three-necked flask equipped with a magnetic rotor and condenser were added 2-bromopyrazole (7.38 g, 30 mmol, 1.0 equiv.), cuprous iodide (113.8 mg, 0.3 mmol, 0.01 equiv.), 1-methylimidazole (49.26 mg, 0.6 mmol, 0.02 equiv.), lithium tert-butoxide (4.84 g, 60 mmol, 2.0 equiv.) in that order. Nitrogen was purged three times, then 2-bromo-4-tert-butylpyridine (7.71 g, 36 mmol, 1.2 equivalents), 1-methylimidazole (49.3 mg, 0.6 mmol, 0.02 equivalents), and 50 mL of toluene were added using a syringe, and the oil bath temperature was raised to 130 ℃ for reaction for 24 hours. Cooling to room temperature, vacuum distilling, removing solvent, then dry loading, separating and purifying by silica gel column chromatography column with eluent of petroleum ether/ethyl acetate =20:1, to obtain 11.31 g of white solid with 99% yield.¹H NMR (500 MHz, DMSO-d ₆): δ 1.39 (s, 9H), 7.45 – 7.56 (m, 3H), 7.37 (t, J = 7.5 Hz, 1H), 7.72 (d, J = 8.4Hz, 2H), 7.94 (d, J = 1.5 Hz, 1H), 8.23 (d, J = 8.0 Hz, 1H), 8.27–8.31 (m, 1H), 8.66 (d, J = 5.0 Hz, 1H)。

Synthesis of intermediate 2: to a 100 mL dry three-necked flask equipped with a magnetic rotor and condenser was added 4-bromopyrazole (3.67 g, 25.0 mmol, 1.0 equiv.), cuprous iodide (476.1 mg, 2.5 mmol, 0.1 equiv.), L-proline (575.6 mg, 5.0 mmol, 0.2 equiv.), K-proline (3.67 mg, 25.0 mmol, 0.0 equiv.), and K-proline in that order₂CO₃ (10.36 g, 90.0 mmol, 3.0 equiv.). Nitrogen was purged three times, and then m-iodoanisole (7.02 g, 30 mmol, 1.2 eq.), solvent DMSO (30 mL), oil bath temperature was raised to 110 ℃ for 2 days. Cooling to room temperature, extracting with ethyl acetate and water three times, combining the organic phases, and adding Na₂SO₄The organic phase was dried and then filtered, the filter cake was washed with ethyl acetate, distilled under reduced pressure to remove the solvent, and the sample was loaded by dry method and separated and purified by silica gel column chromatography, eluting with petroleum ether/ethyl acetate =20:1 to give 5.66g of oily liquid with a yield of 89%. Directly used for the next reaction.

Synthesis of intermediate 3: to the direction ofA250 mL dry three-necked bottle with a magnetic rotor and a condenser is sequentially added with pinacol diboron (5.37 g, 23.3 mmol, 1.1 equivalent) and [1, 1' -bis (diphenylphosphino) ferrocene]Palladium dichloride dichloromethane complex (PdCl)₂(dppf)﹒CH₂Cl₂) (519.4 mg, 0.64 mmol, 0.03 equiv.), potassium acetate (6.30 g, 63.6 mmol, 3.0 equiv.). Nitrogen was purged three times, then intermediate 2 (5.37 g, 21.2 mmol, 1.0 equiv) solvent DMSO (30 mL) was added with a syringe and the oil bath temperature was raised to 80 ℃ for 3 days. Cooled to room temperature, diluted with ethyl acetate and filtered on a buchner funnel, and the filter cake was washed with ethyl acetate. Extracting with ethyl acetate and water for three times, mixing organic phases, and extracting with anhydrous Na₂SO₄Drying the organic matter, filtering, distilling under reduced pressure, removing the solvent, loading the sample by a dry method, and separating and purifying by a silica gel column chromatography chromatographic column, wherein the eluent is petroleum ether/ethyl acetate =20:1, and 3.59 g of white solid is obtained, and the yield is 57%.¹H NMR (500 MHz, DMSO-d ₆): δ 1.29 (s, 12H), 3.83 (s, 3H), 6.88 (ddd, J = 8.5, 2.5, 1.0 Hz, 1H), 7.37 (t, J = 8.0 Hz, 1H), 7.47-7.50 (m, 2H), 7.85 (s, 1H), 8.78 (s, 1H)。

Synthesis of intermediate 4: to a 500 mL dry three-necked flask with a magnetic rotor and condenser was added 2-amino-4-bromo-benzoic acid (21.60 g, 100 mmol), methanol (300 mL), 98% H in that order₂SO₄(80 mL), the oil bath temperature was raised to 70 ℃ for 2 days. Cooled to room temperature and neutralized with NaOH to 6-7, then extracted three times with ethyl acetate and dried over Na₂SO₄The organic phase was dried and then filtered, distilled under reduced pressure to remove the solvent, then the poor solvent hexane was added, recrystallized 2 times, and then the mixture was filtered using a buchner funnel to give product 4 as a white solid 17.98g with a yield of 78%. Directly used for the next reaction.

Synthesis of intermediate 5: to a 100 mL dry three-necked flask with a magnetic rotor and condenser was added in order intermediate 4 (6.90 g, 30 mmol, 1.0 equiv.), phenylboronic acid (3.84 g, 31.5 mmol, 1.05 equiv.), tetrakis (triphenylphosphine) palladium (Pd (PPh)₃)₄ ) (1.04 g, 0.9 mmol, 0.03 eq.), K₂CO₃ (8.29 g, 60 mmol, 2.0 equiv.), the nitrogen was purged three times and 1, 4-dioxane (30 mL) and H were added under nitrogen blanket₂O (15 mL). The oil bath temperature is raised to 100 ℃ and the reaction is stirred for 6.0 hours, cooled to room temperature, extracted three times with 30 mL ethyl acetate and then extracted with anhydrous Na₂SO₄The organic phase was dried, filtered, distilled under reduced pressure to remove the solvent, dry loaded, and purified by column chromatography on silica gel with eluent petroleum ether/ethyl acetate =20:1 to give 4.81 g of white solid in 76% yield.¹H NMR (500 MHz, CDCl₃) δ 3.92 (s, 3H), 5.80 (s, 2H), 6.77 (d, J = 8.5 Hz, 1H), 7.27–7.33 (m, 1H), 7.40–7.45 (m, 2H), 7.55–7.59 (m, 3H), 8.15 (d, J = 2.5 Hz, 1H)。

Synthesis of intermediate 6: to a 250 mL dry three-necked flask with a magnetic rotor and condenser was added in the order intermediate 5 (4.46 g, 19.7 mmol, 1.0 eq.), H₂O (20 mL), HCl (8 mL), and stirred at room temperature for 2 hours. Then adding sodium nitrite (NaNO)₂) (1.49 g, 21.6 mmol, 1.1 equiv.) was dissolved in 3 mL of water and slowly added dropwise to the reaction system and stirred at 0 ℃ for 1.0 hour, and finally potassium iodide (KI) (3.91 g, 23.6 mmol, 1.2 equiv.) was dissolved in 3 mL of water and slowly added dropwise to the reaction system at 0 ℃ and slowly returned to room temperature for 5.0 hours. After the reaction is finished, sodium thiosulfate (Na) is added₂S₂O₃) The reaction was quenched and extracted three times with ethyl acetate, the organic phases combined and washed with anhydrous Na₂SO₄Drying the organic phase, filtering, distilling under reduced pressure to remove the solvent, loading the sample by a dry method, and separating and purifying by a silica gel column chromatography column, wherein the eluent is petroleum ether to obtain 2.35 g of red oily substance with the yield of 35%.¹H NMR (500 MHz, CDCl₃) δ 3.98 (s, 3H), 7.38–7.42 (m, 2H), 7.46-7.49 (m, 2H), 7.59 (s, 1H), 7.597-7.603 (m, 1H), 8.04 (d, J = 2.5 Hz, 1H), 8.07 (d, J = 8.0 Hz, 1H)。

Synthesis of intermediate 7: to a 100 mL dry three-necked flask equipped with a magnetic rotor and a condenser was added in the order intermediate 6(4.06 g, 12.0 mmol, 1.0 equiv.), intermediate 3(3.64 g, 12 mmol, 1.0 equivalent)Amount), Pd (PPh)₃)₄ (694.5 mg, 0.6 mmol, 0.05 eq.), Potassium carbonate (K)₂CO₃) (3.32 g, 24.4 mmol, 2.0 equiv.), the nitrogen was purged three times and 1, 4-dioxane (25 mL) and H were added under nitrogen blanket₂O (10 mL). The oil bath temperature was raised to 100 ℃ and the reaction was stirred for 12 hours, cooled to room temperature, extracted with ethyl acetate (30 mL. times.3), and extracted with anhydrous Na₂SO₄Drying the organic phase, filtering with a funnel, distilling under reduced pressure, removing the solvent, loading the sample by a dry method, and separating and purifying with a silica gel column chromatography column, wherein the eluent is petroleum ether/ethyl acetate =20:1, and light yellow oily matter 1.65 g is obtained, and the yield is 36%.¹H NMR (500 MHz, DMSO-d ₆) δ 3.83 (s, 3H), 3.86 (s, 3H), 6.91–6.93 (m, 1H), 7.42–7.478 (m, 2H), 7.481–7.53 (m, 4H), 7.73 (d, J = 8.0 Hz, 1H), 7.76 (d, J = 7.5 Hz, 2H), 7.85 (s, 1H), 7.92 (dd, J = 8.0, 2.0 Hz, 1H), 8.00 (d, J = 2.0 Hz, 1H), 8.79 (s, 1H)。

Synthesis of intermediate 8: to a 100 mL dry three-necked flask with a magnetic rotor and condenser was added in order intermediate 7(1.68 g, 4.3 mmol, 1.0 equiv.), the nitrogen was purged three times, and then methylmagnesium bromide (MeMgBr) (26.6 mL, 26.6 mmol, 6.2 equiv.) was added under nitrogen, and the reaction was stirred at 40 ℃ for 3 days. Quenching the reaction by adding ammonium chloride, extracting with ethyl acetate three times, and adding anhydrous Na₂SO₄Drying the organic phase, then filtering, distilling under reduced pressure, removing the solvent, loading the sample by a dry method, and separating and purifying by adopting a silica gel column chromatography column, wherein the eluent is petroleum ether: ethyl acetate =10:1, giving 1.41 g of a pale yellow oil, yield 85%.¹H NMR (500 MHz, DMSO-d ₆) δ 1.43 (s, 6H), 3.85 (s, 3H), 5.14 (s, 1H), 6.91–6.87 (m, 1H), 7.27 (d, J = 7.5 Hz, 1H), 7.37–7.44 (m, 2H), 7.46–7.48 (m, 2H), 7.48–7.52 (m, 2H), 7.54 (dd, J = 8.0, 2.0 Hz, 1H), 7.70 (dd, J = 8.0, 1.0 Hz, 2H), 8.03 (d, J = 2.0 Hz, 1H), 7.84 (s, 1H), 8.61 (s, 1H)。

Synthesis of intermediate 9: adding intermediate 8 (to a 100 mL dry three-necked flask with a magnetic rotor and a condenser tube1.42 g, 3.7 mmol, 1.0 eq), nitrogen was purged three times and HBr (48%) (10 mL), acetic acid (5 mL) at 120 deg.C under nitrogen blanket was added^oStirring for 3 days, cooling to room temperature, distilling under reduced pressure to remove solvent, adding 20 mL of water, neutralizing with NaOH aqueous solution to pH 6-7, extracting with ethyl acetate for three times, combining organic phases, and adding anhydrous Na₂SO₄Drying, filtering, distilling under reduced pressure, removing solvent, loading by dry method, separating and purifying by silica gel column chromatography, eluting with petroleum ether: ethyl acetate =5:1, yielding 628.1 mg of white solid in 47% yield.¹H NMR (500 MHz, DMSO-d6) δ 1.52 (s, 6H), 6.88 (ddd, J = 8.5, 2.5, 1.0 Hz, 1H), 7.02–7.08 (m, 2H), 7.33–7.40 (m, 2H), 7.47 (t, J = 8.0 Hz, 2H), 7.70–7.73 (m, 2H), 7.54–7.60 (m, 2H), 7.78 (d, J = 1.5 Hz, 1H), 7.87 (s, 1H), 9.99 (s, 1H)。

Synthesis of ligand 3: to a 100 mL dry three-necked flask equipped with a magnetic rotor and condenser were added in order intermediate 9 (628.1 mg, 1.8 mmol, 1.0 equiv.), intermediate 1(743.5 mg, 1.9 mmol, 1.1 equiv.), cuprous iodide (33.9 mg, 0.17 mmol, 0.01 equiv.), 2-picolinic acid (44 mg, 0.36 mmol, 0.02 equiv.), K₃PO₄(755.7 mg, 3.56 mmol, 2.0 equiv.). The nitrogen was purged three times, then the solvent DMSO (10 mL) was added under nitrogen protection at 120 deg.C^oC reaction stirred 24 hours, cooled to room temperature, extracted three times with 30 mL ethyl acetate and water, over anhydrous Na₂SO₄The organic phase was dried, filtered, distilled under reduced pressure to remove the solvent, dry loaded, and purified by column chromatography on silica gel with eluent petroleum ether/ethyl acetate =10:1 to give 694.0 mg of white solid in 60% yield.¹H NMR (500 MHz, DMSO-d ₆) δ 1.31 (s, 9H), 1.34 (s, 6H), 7.19 (dd, J = 8.5, 2.0 Hz, 1H), 7.23 (t, J = 2.0 Hz, 1H), 7.27 (dd, J = 8.0, 1.5 Hz, 1H), 7.32–7.37 (m, 2H), 7.44–7.49 (m, 6H), 7.52 (d, J = 8.0 Hz, 1H), 7.55 (dd, J = 8.0, 2.0 Hz, 1H), 7.62 (t, J = 8.0 Hz, 1H), 7.68 (dd, J = 7.0, 1.5 Hz, 4H), 7.76 (d, J= 8.5 Hz, 1H), 7.86 (s, 1H), 8.25 (d, J = 7.5 Hz, 1H), 8.33 (d, J = 8.5 Hz, 1H), 8.58 (d, J = 5.5 Hz, 1H)。

Synthesis of Pt 3: to a 100 mL dry three-necked flask equipped with a magnetic rotor and condenser was added ligand 1(330.0 mg, 0.5 mmol, 1.0 eq.) and n-butylammonium bromide (N-butylammonium bromide) ⁿ Bu₄NBr) (16.4 mg, 0.05 mmol, 0.01 equiv.), Potassium tetrachloroplatinate (K)₂PtCl₄) (232.8 mg, 0.56 mmol, 1.1 eq.) nitrogen is purged three times and then solvent acetic acid (30 mL) is added, after bubbling nitrogen for 30 minutes, the reaction mixture is stirred at room temperature for 15 hours and then at 110 deg.C^oStirring for 2 days under C. The reaction mixture was cooled to room temperature, the solvent was removed by distillation under the reduced pressure, and the resulting crude product was purified by silica gel column chromatography with an eluent (petroleum ether/dichloromethane =5: 1) to obtain 91.0 mg of a yellow solid in a yield of 21%.¹H NMR (500 MHz, DMSO-d ₆) δ 1.41 (s, 9H), 1.90 (s, 6H), 7.04 (d, J = 8.0 Hz, 1H), 7.23 (d, J = 8.0 Hz, 1H), 7.36–7.45 (m, 3H), 7.48–7.55 (m, 3H), 7.57 (dd, J = 6.5, 2.0 Hz, 1H), 7.61 (d, J = 7.5 Hz, 1H), 7.69 (dd, J = 7.5, 1.5 Hz, 1H), 7.73–7.81 (m, 3H), 7.89 (d, J = 8.5 Hz, 1H), 7.97 (d, J = 1.5 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 8.19 (t, J = 2.0 Hz, 2H), 8.50 (s, 1H), 9.24 (d, J = 6.5 Hz, 1H)。

FIG. 1 shows a room-temperature emission spectrum of Pt3 as a platinum complex in the embodiment in a methylene chloride solution and a low-temperature (77K) emission spectrum in 2-methyltetrahydrofuran. As can be seen from the comparison of the Pt3 complex at room temperature and 77K, the T of 77K is₁→S₀Has a radiation peak at about 472nm and a triplet energy level of about 2.63 eV; and an emission peak at about 476nm of the room temperature spectrum is T₁→S₀The peak of (a) is a phosphorescence emission peak; and a main emission peak at about 448nm is a deep blue emission peak, which is S₁→S₀The peak of (2) is a delayed fluorescence emission peak. The resultant molecules with low triplet state energy level can realize blue light emission.

As shown in fig. 8, through a linking group willPhenyl Ar¹After linking with pyrazolyl, the intensity of delayed fluorescence at 449nm can be greatly increased to more than 1.5 times of that of a control molecule, so that the blue chromaticity of the luminescent material Pt3 is higher.

Example 2: the platinum complex Pt14 can be synthesized by the following route:

synthesis of intermediate 10: to a 100 mL dry three-necked flask equipped with a magnetic rotor and condenser was added in order intermediate 4 (6.90 g, 30 mmol, 1.0 eq.), 2, 5-dimethylphenylboronic acid (3.84 g, 31.5 mmol, 1.05 eq.), Pd (PPh)₃)₄ (1.04 g, 0.9 mmol, 0.03 eq.), K₂CO₃ (8.29 g, 60 mmol, 2.0 equiv.), the nitrogen was purged three times and 1, 4-dioxane (30 mL) and H were added under nitrogen blanket₂O (15 mL). The oil bath temperature is raised to 100 ℃ and the reaction is stirred for 6.0 hours, cooled to room temperature, extracted three times with 30 mL ethyl acetate and then extracted with anhydrous Na₂SO₄The organic phase was dried, filtered, distilled under reduced pressure to remove the solvent, dry loaded, and purified by column chromatography on silica gel with eluent petroleum ether/ethyl acetate =20:1 to give 5.29 g of white solid with a yield of 69%. Directly used for the next reaction.

Synthesis of intermediate 11: to a 250 mL dry three-necked flask with a magnetic rotor and condenser was added in the order intermediate 10 (4.96 g, 19.6 mmol, 1.0 eq.), H₂O (20 mL), HCl (8 mL), and stirred at room temperature for 2 h. Then NaNO is added₂(1.47 g, 21.6 mmol, 1.1 equiv.) was dissolved in 3 mL of water and slowly added dropwise to the reaction system and stirred at 0 ℃ for 1.0 hour, and finally KI (3.87 g, 23.6 mmol, 1.2 equiv.) was dissolved in 3 mL of water and slowly added dropwise to the reaction system at 0 ℃ and slowly returned to room temperature for 5.0 hours. After the reaction is finished, sodium thiosulfate (Na) is added₂S₂O₃) The reaction was quenched and extracted three times with ethyl acetate, the organic phases combined and washed with anhydrous Na₂SO₄Drying the organic phase, then filtering, distilling under reduced pressure,removing solvent, loading by dry method, separating and purifying by silica gel column chromatography column, eluting with pure petroleum ether to obtain red oily substance 4.95 g with yield of 69%.¹H NMR (500 MHz, CDCl₃) δ 2.04 (s, 6H), 3.94 (s, 3H), 6.99 (dd, J = 8.0, 2.0 Hz, 1H), 7.13 (t, J = 3.5Hz, 2H), 7.20 (t, J = 8.0 Hz 1H), 7.65 (d, J = 2.0 Hz, 1H), 8.07 (d, J = 8.0 Hz, 1H)。

Synthesis of intermediate 12: to a 100 mL dry three-necked flask equipped with a magnetic rotor and condenser was added in the order intermediate 11 (2.13 g, 5.8 mmol, 1.0 equiv.), intermediate 3 (1.74 g, 5.8 mmol, 1.0 equiv.), Pd (PPh)₃)₄ (335.7 mg, 0.3 mmol, 0.05 eq.), K₂CO₃ (1.61 g, 11.6 mmol, 2.0 equiv.), the nitrogen was purged three times and 1, 4-dioxane (20 mL) and H were added under nitrogen blanket₂O (10 mL). The oil bath temperature is raised to 100 ℃ and the reaction is stirred for 12 hours, cooled to room temperature, extracted three times with 30 mL ethyl acetate and then extracted with anhydrous Na₂SO₄The organic phase was dried, filtered, distilled under reduced pressure to remove the solvent, loaded on a dry method, and purified by column chromatography on silica gel with petroleum ether/ethyl acetate =20:1 to give 2.19 g of pale yellow oil with a yield of 40%.¹H NMR (500 MHz, DMSO-d ₆) δ 2.03 (s, 6H), 3.78 (s, 3H), 3.86 (s, 3H), 6.89–6.94 (m, 1H), 7.14–7.18 (m, 2H), 7.19–7.23 (m, 1H), 7.40–7.46 (m, 2H), 7.47–7.51 (m, 3H), 7.70 (d, J = 8.0 Hz, 1H), 7.87–7.88 (m, 1H), 8.79 (d, J = 0.5 Hz, 1H)。

Synthesis of intermediate 13: to a 100 mL dry three-necked flask with magnetic rotor and condenser was added in sequence intermediate 12 (1.74 g, 4.1 mmol, 1.0 equiv.), purged with nitrogen three times, and then added MeMgBr (25.4 mL, 25.4 mmol, 6.2 equiv.) under nitrogen protection at 40.4 mL^oC reaction stirred for 3 days. Addition of NH₄The reaction was quenched with Cl, extracted three times with ethyl acetate, and extracted with anhydrous Na₂SO₄Drying the organic phase, filtering, distilling under reduced pressure to remove solvent, loading, separating and purifying with silica gel column chromatography column, eluting with petroleumEther: ethyl acetate =10:1, giving 1.35 g of a light yellow oil, yield 80%.¹H NMR (500 MHz, DMSO-d ₆) δ 1.41 (s, 6H), 2.04 (s, 6H), 3.85 (s, 3H), 5.03 (s, 1H), 6.86–6.91 (m, 1H), 7.04 (dd, J = 8.0, 2.0 Hz, 1H), 7.12–7.20 (m, 3H), 7.26 (d, J = 7.5 Hz, 1H), 7.38–7.44 (m, 1H), 7.46–7.50 (m, 3H), 7.88 (s, 1H), 8.68 (s, 1H)。

Synthesis of intermediate 14: to a 100 mL dry three-necked flask with magnetic rotor and condenser was added intermediate 13 (1.20 g, 2.9 mmol, 1.0 eq.), the nitrogen was purged three times, and 48% HBr (10 mL), HAOc (5 mL) under nitrogen blanket at 120 deg.C^oC reaction is stirred for 3 days, cooled to room temperature, then decompressed and distilled to remove the solvent, then 20 mL of water is added, and neutralized to pH 6-7 by NaOH aqueous solution, then extraction is carried out for three times by ethyl acetate, organic phases are combined, and anhydrous Na is used₂SO₄Drying, filtering, distilling under reduced pressure, removing solvent, loading by dry method, separating and purifying by silica gel column chromatography, eluting with petroleum ether: ethyl acetate =: 5:1, 938.2 mg of a white solid was obtained, yield 84%.¹H NMR (500 MHz, DMSO-d ₆) δ 1.47 (s, 6H), 2.02 (s, 6H), 6.84–6.90 (m, 1H), 6.99–7.08 (m, 3H), 7.10–7.19 (m, 3H), 7.26 (t, J = 4.0 Hz, 1H), 7.37 (t, J = 8.0 Hz, 1H), 7.47–7.59 (m, 1H), 7.86 (d, J = 5.5 Hz, 1H), 9.96 (s, 1H)。

Synthesis of ligand 14: to a 100 mL dry three-necked flask equipped with a magnetic rotor and condenser were added in order intermediate 14 (938.2 mg, 2.5 mmol, 1.0 equiv.), intermediate 1 (1.10 g, 2.7 mmol, 1.1 equiv.), cuprous iodide (47.0 mg, 0.25 mmol, 0.01 equiv.), 2-picolinic acid (60.9 mg, 0.50 mmol, 0.02 equiv.), K₃PO₄(1.05 g, 4.9 mmol, 2.0 equiv.). The nitrogen was purged three times, then the solvent dimethyl sulfoxide (10 mL) was added under nitrogen protection at 120 deg.C^oC reaction stirred 24 hours, cooled to room temperature, extracted three times with 30 mL ethyl acetate and water, over anhydrous Na₂SO₄Drying the organic phase, filtering, distilling under reduced pressure to remove solvent, loading by dry method, and performing silica gel column chromatographySeparating and purifying by chromatography column with eluting agent of petroleum ether/ethyl acetate =10:1 to obtain white solid 914.4 mg with 55% yield.¹H NMR (500 MHz, DMSO-d ₆) δ 1.28 (s, 15H), 1.98 (s, 6H), 6.99 (dd, J = 7.5, 1.5 Hz, 1H), 7.09–7.14 (m, 2H), 7.14–7.17 (m, 2H), 7.18 (m, 1H), 7.22 (t, J = 2.0 Hz, 1H), 7.26 (dd, J = 7.5, 2.0 Hz, 1H), 7.34 (t, J = 7.0 Hz, 1H), 7.42–7.48 (m, 4H), 7.50 (d, J = 7.5 Hz, 1H), 7.61 (t, J = 8.0 Hz, 1H), 7.67 (d, J = 1.5 Hz, 1H), 7.74 (d, J = 8.0 Hz, 1H), 7.85 (s, 1H), 8.24 (d, J= 7.5 Hz, 1H), 8.32 (d, J = 8.0 Hz, 1H), 8.56 (d, J = 5.0 Hz, 1H)。

Synthesis of Pt 14A 100 mL dry three-necked flask equipped with a magnetic rotor and condenser was charged with ligand L14 (500.0 mg, 0.74 mmol, 1.0 equiv) in sequence, ⁿ Bu₄NBr (23.7 mg, 0.07 mmol, 0.01 equiv.), K₂PtCl₄ (337.8 mg, 0.82 mmol, 1.1 equiv.), purging nitrogen three times, adding solvent acetic acid (40 mL), bubbling nitrogen for 30 minutes, stirring the reaction mixture at room temperature for 10 hours, then at 110^oStirring for 2 days under C. The reaction mixture was cooled to room temperature, the solvent was removed by distillation under the reduced pressure, and the resulting crude product was purified by silica gel column chromatography with an eluent (petroleum ether/dichloromethane =5: 1) to obtain 385.1 mg of a yellow solid in a yield of 60%.¹H NMR (500 MHz, DMSO-d ₆) δ 1.41 (s, 9H), 1.85 (s, 6H), 2.06 (s, 6H), 7.03 (d, J = 8.0 Hz, 1H), 7.12–7.21 (m, 4H), 7.23 (d, J = 8.0 Hz, 1H), 7.36 (t, J = 8.0 Hz, 1H), 7.42 (t, J = 7.5 Hz, 1H), 7.47 (d, J = 1.0 Hz, 1H), 7.50–7.55 (m, 1H), 7.55–7.62 (m, 2H), 7.75 (d, J = 7.5 Hz, 1H), 7.89 (d, J = 8.0 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 8.19 (t, J = 2.0 Hz, 2H), 8.49 (s, 1H), 9.24 (d, J = 6.0 Hz, 1H)。

FIG. 2 shows a room-temperature emission spectrum of Pt14 as a platinum complex in the embodiment in a methylene chloride solution and a low-temperature (77K) emission spectrum in 2-methyltetrahydrofuran. T of 77K thereof₁→S₀The main emission peaks of the radiation peak of (2) at 441nm and at room temperature 447nm are both T₁→S₀The radiation of (2) is deep blue phosphorescence; this example illustrates phenyl Ar²The introduction of two methyl groups into the ortho position of the phenyl can obviously increase the dihedral angle between phenyl and phenyl, greatly reduce the conjugation degree of the phenyl and improve the triplet level to 2.81 eV.

Example 3. platinum complex Pt31 can be synthesized as follows:

synthesis of intermediate 15: to a 100 mL dry three-necked flask equipped with a magnetic rotor and a condenser were added in the order of intermediate 4 (5.75 g, 25 mmol, 1.0 equiv), 2-methylphenylboronic acid (3.60 g, 26.3 mmol, 1.05 equiv), Pd (PPh)₃)₄(866.7 mg, 0.75 mmol, 0.03 equiv), K₂CO₃(6.91 g, 50 mmol, 2.0 equiv), nitrogen was purged three times and 1, 4-dioxane (25 mL) and H were added under nitrogen blanket₂O (10 mL). The oil bath temperature is raised to 100 ℃ and stirred for reaction for 6.0 h, the reaction mixture is cooled to room temperature, extracted with 30 mL of ethyl acetate for three times, the organic phase is dried by anhydrous Na2SO4, then filtered, distilled under reduced pressure, the solvent is removed, the sample is loaded by a dry method, and is separated and purified by a silica gel column chromatography chromatographic column, and the eluent is petroleum ether/ethyl acetate =20:1, SO that 4.71 g of white solid is obtained with the yield of 78%.¹H NMR (500 MHz, CDCl₃): δ 2.28 (s, 3H), 3.86 (s, 3H), 5.75 (s, 2H), 6.71 (d, J = 8.5 Hz, 1H), 7.14–7.33 (m, 5H), 7.84 (d, J = 2.0 Hz, 1H)。

Synthesis of intermediate 16: to a 250 mL dry three-necked flask equipped with a magnetic rotor and condenser was added in the order intermediate 15(4.71 g, 19.5 mmol, 1.0 equiv), H₂O (20 mL), HCl (8 mL), and stirred at room temperature for 2 h. Then NaNO is added₂(1.48 g, 21.5 mmol, 1.1 equiv) was dissolved in 3 mL of water and slowly added dropwise to the reaction system at 0 ℃ with stirring for 1.0 h, and finally KI (3.89 g, 23.4 mmol, 1.2 equiv) was dissolved in 3 mL of water and slowly added dropwise to the reaction system at 0 ℃ with slowly returning to room temperatureShould be 5.0 h. After the reaction is finished, Na is added₂S₂O₃The reaction was quenched and extracted three times with ethyl acetate, the organic phases combined and washed with anhydrous Na₂SO₄Drying the organic phase, filtering, distilling under reduced pressure to remove the solvent, loading the sample by a dry method, and separating and purifying by a silica gel column chromatography column, wherein the eluent is petroleum ether to obtain 4.52 g of red oily substance with the yield of 65%.¹H NMR (500 MHz, CDCl₃) δ 2.25 (s, 3H), 3.93 (s, 3H), 7.12 (dd, J = 8.0, 2.0 Hz, 1H), 7.19 (d, J = 7.0 Hz, 1H), 7.22–7.31 (m, 3H), 7.77 (d, J = 2.0 Hz, 1H), 8.02 (d, J =8.0 Hz, 1H)。

Synthesis of intermediate 17: to a 100 mL dry three-necked flask equipped with a magnetic rotor and a condenser tube were added in this order intermediate 16 (2.97 g, 8.4 mmol, 1.0 equiv), intermediate 3(2.78 g, 9.3 mmol, 1.0 equiv), Pd (PPh)₃)₄ (487.1 mg, 0.42 mmol, 0.05 equiv), K₂CO₃(2.33 g, 16.8 mmol, 2.0 equiv), nitrogen was purged three times and 1, 4-dioxane (15 mL) and H were added under nitrogen blanket₂O (5 mL). The oil bath temperature was raised to 100 ℃ and the reaction stirred for 2 days, cooled to room temperature, extracted with ethyl acetate (30 mL X3), over anhydrous Na₂SO₄The organic phase was dried, filtered through a funnel, distilled under reduced pressure to remove the solvent, loaded on a dry method, and purified by silica gel column chromatography with petroleum ether/ethyl acetate =10:1 to give a pale yellow oil 1.91 g with a yield of 57%.¹H NMR (500 MHz, CDCl₃) δ 2.32 (s, 3H), 3.83 (s, 3H), 3.89 (s, 3H), 6.84-6.86 (m, 1H), 7.23–7.32 (m, 5H), 7.33–7.40 (m, 2H), 7.46–7.54 (m, 2H), 7.76 (d, J = 1.5 Hz, 1H), 7.84 (s, 1H), 8.14 (d, J = 0.5 Hz, 1H)。

Synthesis of intermediate 18: to a 100 mL dry three-necked flask with magnetic rotor and condenser was added in sequence intermediate 17(1.91 g, 5.0 mmol, 1.0 equiv), nitrogen was purged three times, and then MeMgBr (31.2 mL, 31.2 mmol, 6.2 equiv) was added under nitrogen blanket at 40^oC reaction stirred for 3 days. Addition of NH₄The reaction was quenched with Cl, extracted three times with ethyl acetate, and extracted with anhydrous Na₂SO₄Drying the organic phase, then filtering, distilling under reduced pressure, removing the solvent, loading the sample by a dry method, and separating and purifying by adopting a silica gel column chromatography column, wherein the eluent is petroleum ether: ethyl acetate =10:1, giving 1.69 g of a light yellow oil, yield 84%.¹H NMR (500 MHz, DMSO-d ₆) δ 2.30 (s, 3H), 3.34 (s, 6H), 3.85 (s, 3H), 5.08 (s, 1H), 8.65 (s, 1H), 6.87-6.89 (m, 1H), 7.20–7.35 (m, 6H), 7.38–7.44 (m, 1H), 7.44–7.52 (m, 2H), 7.70 (s, 1H), 7.87 (s, 1H)。

Synthesis of intermediate 19: to a 100 mL dry three-necked flask with magnetic rotor and condenser was added intermediate 8(1.68 g, 4.2 mmol, 1.0 equiv), the nitrogen was purged three times, and then HBr (48%) (100 mL), acetic acid (5 mL) under nitrogen blanket was added at 120 deg.C^oC reaction stirred for 3 days, cooled to room temperature, then reduced pressure distilled to remove solvent, then added 20 mL water, and Na₂CO₃Neutralizing until no air bubble is generated, extracting with ethyl acetate for three times, combining organic phases, and extracting with anhydrous Na₂SO₄Drying, filtering, distilling under reduced pressure, removing solvent, loading by dry method, separating and purifying by silica gel column chromatography column with eluent of ethyl acetate/methanol =20:1 to obtain white solid 1.23 g with yield 79%. Directly used for the next reaction.

Synthesis of ligand L31: to a 100 mL dry three-necked flask equipped with a magnetic rotor and a condenser were added in this order intermediate 19 (1.23 g, 3.4 mmol, 1.0 equiv), intermediate 1 (1.40 g, 3.7 mmol, 1.1 equiv), cuprous iodide (63.9 mg, 0.34 mmol, 0.01 equiv), 2-picolinic acid (82.73 mg, 0.67 mmol, 0.02 equiv), K₃PO₄(1.43 mg, 6.7 mmol, 2.0 equiv). The nitrogen was purged three times, then the solvent DMSO (15 mL) was added under nitrogen protection at 115^oC reaction is stirred for 24 hours, cooled to room temperature, diluted by 30 mL ethyl acetate, filtered by a Buchner funnel, filter cake is washed by 100 mL ethyl acetate, organic phase is extracted by adding 30 mL water for three times, and finally anhydrous Na is used₂SO₄The organic phase was dried and Na was filtered off₂SO₄Distilling under reduced pressure, removing solvent, dry loading, and performing silica gel column chromatographyThe column was purified with an eluent of petroleum ether/ethyl acetate =10:1 to give 475.0 mg of a white solid with 21% yield.¹H NMR (500 MHz, DMSO-d ₆) δ 1.28 (s, 9H), 1.30 (s, 6H), 2.24 (s, 3H), 7.16–7.30 (m, 8H), 7.34 (dd, J = 10.5, 1.5 Hz, 2H), 7.41–7.50 (m, 5H), 7.61 (t, J = 8.0 Hz, 1H), 7.67 (d, J = 1.5 Hz, 1H), 7.74 (d, J = 8..5 Hz, 1H), 7.85 (s, 1H), 8.24 (d, J = 7.5 Hz, 1H), 8.31 (d, J = 8.5 Hz, 1H), 8.56 (d, J = 5.5 Hz, 1H)。

Synthesis of Pt 31: add ligand 1(400.0 mg, 0.6 mmol, 1.0 equiv) sequentially to a 100 mL dry three-necked flask with magnetic rotor and condenser, ⁿ Bu₄NBr (19.3 mg, 0.06 mmol, 0.01 equiv), K₂PtCl₄ (274.7 mg, 0.66 mmol, 1.1 equiv), the nitrogen was purged three times, then the solvent acetic acid (30 mL) was added, after bubbling nitrogen for 30 minutes, the reaction mixture was stirred at room temperature for 15 hours, then at 110^oStirring for 3 days under C. The reaction mixture was cooled to room temperature, the solvent was removed by distillation under the reduced pressure, and the resulting crude product was purified by silica gel column chromatography with an eluent (petroleum ether/dichloromethane = 4: 1) to obtain 194.9 mg of a yellow solid in a yield of 38%.¹H NMR (500 MHz, DMSO-d ₆) δ 1.41 (s, 9H), 1.86 (s, 6H), 2.32 (s, 3H), 7.03 (d, J = 8.0 Hz, 1H), 7.22 (d, J = 8.0 Hz, 1H), 7.27 – 7.32 (m, 3H), 7.32 – 7.36 (m, 2H), 7.38 (d, J = 8.0 Hz, 1H), 7.42 (t, J = 7.5 Hz, 1H), 7.52 (t, J = 7.0 Hz, 1H), 7.55 – 7.61 (m, 2H), 7.66 (s, 1H), 7.74 (d, J =8.0 Hz, 1H), 7.89 (d, J = 8.5 Hz, 1H), 8.12 (d, J = 8.5 Hz, 1H), 8.18 (d, J = 7.5 Hz, 2H), 8.50 (s, 1H), 9.23 (d, J = 6.5 Hz, 1H)。

FIG. 3 is a room temperature emission spectrum of a platinum complex Pt31 in a dichloromethane solution and a 77K emission spectrum in 2-methyltetrahydrofuran.

The emission spectra of the platinum complex Pt14 and the platinum complex Pt31 are blue-shifted by 1-2nm relative to the control, and have a bluer deep blue characteristic.

Example compounds of the invention, whether phenyl Ar²Whether the ortho-position of (A) contains a non-hydrogen substituent or not can realize deep blue luminescence.

From fig. 4-7, it can be seen that there is no significant difference in the energy level distributions of several platinum complexes, which have very similar HOMO, LUMO properties. Phenyl Ar in Compounds of the invention²Whether or not there is a non-hydrogen substituent in the ortho position, the effect on HOMO, LUMO properties is not significant.

While the foregoing is directed to embodiments of the present invention, it will be understood by those skilled in the art that various changes may be made without departing from the spirit and scope of the invention.

Claims (5)

1. A tetradentate ring metal platinum (II) complex containing bridged phenyl-pyrazole building blocks, wherein the platinum complex has a structure represented by general formula (IV), (V):

wherein R is¹、R²、R⁶、R⁷、R⁸、R¹⁰And R¹¹Each independently hydrogen, deuterium, aryl, cycloalkyl, alkyl, or a combination thereof; adjacent said R¹、R²、R⁶、R⁷、R⁸、R¹⁰And R¹¹May be linked to form a fused ring; r³、R⁴、R⁵And R⁹Each independently is hydrogen or deuterium;

R^a、R^b、R^c、R^deach independently hydrogen, deuterium, aryl, cycloalkyl, alkyl, or a combination thereof;

s represents an integer of 0 to 5, m and n each independently represents an integer of 0 to 4, o represents an integer of 0 to 2, p and r each independently represents an integer of 0 to 3, and q represents an integer of 0 to 1.

2. Use of the tetradentate cyclometalated platinum (II) complexes containing bridged phenyl-pyrazole structural units as claimed in claim 1 in electroluminescent devices.

3. A device comprising a tetradentate cyclometalated platinum (II) complex containing a bridged phenyl-pyrazole building block as claimed in claim 1.

4. The device of claim 3, wherein the device is a photovoltaic device, a light emitting display device.

5. The device of claim 3 comprising at least one cathode, at least one anode and at least one light emitting layer, at least one of said light emitting layers comprising a tetradentate cyclometalated platinum (II) complex comprising bridged phenyl-pyrazole building blocks as described in claim 1.

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