CN115850344A

CN115850344A - Organic light emitting diode material, device and apparatus

Info

Publication number: CN115850344A
Application number: CN202211523366.8A
Authority: CN
Inventors: 李贵杰; 湛丰; 佘远斌
Original assignee: Zhejiang University of Technology ZJUT; Zhejiang Huadisplay Optoelectronics Co Ltd
Current assignee: Zhejiang University of Technology ZJUT; Zhejiang Huadisplay Optoelectronics Co Ltd
Priority date: 2022-11-30
Filing date: 2022-11-30
Publication date: 2023-03-28

Abstract

The invention relates to an organic light emitting diode material, an organic light emitting diode device and an organic light emitting diode device. The phosphorescent material and the composition have good chemical stability, can improve and balance the transport of holes and electrons, and enable the energy transmission between a host and an object to be more efficient, and the composition has the advantages of improving the current efficiency and the service life of an organic electroluminescent device, and has great application prospects in the fields of OLED display and illumination.

Description

Organic light emitting diode material, device and apparatus

Technical Field

The invention belongs to the field of organic electroluminescence, and particularly relates to an organic light-emitting diode material, a device and a device, wherein an object is a quadridentate ring metal platinum (II) complex phosphorescent material based on pyridocarbene coordination, or a boron-containing organic molecular luminescent material sensitized by the quadridentate ring metal platinum (II) complex phosphorescent material.

Background

Organic Light-Emitting diodes (OLEDs) are a new generation of full-color display and illumination technologies. Compared with the defects of low response speed, small visual angle, backlight source requirement, high energy consumption and the like of liquid crystal display, the OLED is used as an autonomous light-emitting device, does not need the backlight source and saves energy; the driving voltage is low, the response speed is high, the resolution and the contrast ratio are high, the visual angle is wide, and the low-temperature performance is outstanding; the OLED device can be made thinner and can be made into flexible structures. In addition, the method also has the advantages of low production cost, simple production process, large-area production and the like. Therefore, the OLED has wide and huge application prospect in the aspects of high-end electronic products and aerospace; with the gradual increase of investment, further development and upgrading of production equipment, OLEDs have a very wide application scene and development prospect in the future.

The core of the development of OLEDs is the design and development of light emitting materials. In early OLED devices, the light-emitting material was mainly organic small molecule fluorescent material. Spin statistical quantum, however, indicates that in the case of electroluminescence, singlet excitons and triplet excitons (exiton) are generated in 25% and 75%, respectively, and since conventional fluorescent materials can only utilize excitons in the singlet state, the maximum theoretical internal quantum efficiency is only 25%, and the remaining 75% of triplet excitons are lost by nonradiative transition. The phosphor electroluminescence of heavy metal organic complex molecules at room temperature was discovered in 1998 by professor Forrest of princeton university, usa and by Thompson of university, southern california. Due to the strong spin-orbit coupling effect of heavy metal atoms, excitons can be more easily subjected to intersystem crossing (ISC) from singlet states to triplet states, so that the OLED device can fully utilize all singlet and triplet excitons generated by electric excitation, and the theoretical internal quantum efficiency of the luminescent material can reach 100% (Nature, 1998,395, 151).

The light-emitting layer in the currently applied OLED device almost completely uses a host-guest light-emitting system mechanism, namely, a guest light-emitting material is doped in a host material, the energy system of the host material is generally larger than that of the guest light-emitting material, and the energy is transferred from the host material to the guest material, so that the guest material is excited to emit light. Commonly used organic phosphorescent guest materials are typically heavy metalsAtoms such as iridium (III), platinum (II), pd (II) and the like. The commonly used phosphorescent organic materials mCBP (3, 3' -bis (9-carbazolyl) -biphenyl) and 2,6-mCPy (2, 6-bis (9-carbazolyl) -pyridine) have high efficiency and high triplet energy levels, which, when used as an organic material, can be efficiently transferred from a light-emitting organic material to a guest phosphorescent light-emitting material. However, due to the characteristic that mCBP is easy to transport holes and electrons are difficult to flow, 2,6-mCPy has poor hole transport, so that the charges in the light-emitting layer are not balanced, and the current efficiency of the device is reduced. In addition, the currently applied heavy metal phosphorescent organic complex molecule cyclometalated iridium (III) complex molecule is limited in number. The content of metal platinum element in the earth crust and the annual output worldwide are about ten times of metal iridium element, and the IrCl used for preparing iridium (III) complex phosphorescent material ₃ ^. H ₂ The price of O (1100 RMB/g) is much higher than that of PtCl for preparing platinum (II) complex phosphorescent material ₂ (210 RMB/g); in addition, the preparation of the iridium (III) complex phosphorescent material relates to four-step reaction comprising iridium (III) dimer, iridium (III) intermediate ligand exchange, mer-iridium (III) complex synthesis and mer-to fac-iridium (III) complex isomer conversion, so that the total yield is greatly reduced, and the raw material IrCl is greatly reduced ₃ ^. H ₂ The utilization rate of O improves the preparation cost of the iridium (III) complex phosphorescent material. In contrast, the preparation of the platinum (II) complex phosphorescent material only has the reaction of platinum salt designed by the metallization of the ligand in the last step, the utilization rate of the platinum element is high, and the preparation cost of the platinum (II) complex phosphorescent material can be further reduced. In summary, the preparation cost of the platinum (II) complex phosphorescent material is far lower than that of the iridium (III) complex phosphorescent material. However, the development of platinum complex materials and devices still has some technical difficulties, and how to improve the efficiency and the service life of the devices is an important research problem. There is therefore a great need to develop novel phosphorescent metal platinum (II) complexes.

Disclosure of Invention

The invention aims to provide one or more guest phosphorescent materials and host materials applied to a light emitting layer of an organic electroluminescent device, a combination of the guest phosphorescent materials and the host materials, and the organic electroluminescent device comprising the combination. The invention finds that the combination of the specific host material and the guest phosphorescent material can improve the current efficiency of the organic electroluminescent device, improve the service life of the device and reduce the operating voltage of the device.

The present invention provides one or more platinum (II) complexes represented by the structural formula Pt (I) or Pt (II) as follows:

wherein:

in the formulae Pt- (I) and Pt- (II), R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ Each independently represents mono-, di-, tri-, tetra-, or unsubstituted;

R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ and R ⁶ Each independently represents any one of hydrogen, deuterium, C1-C30 alkyl, C1-C30 haloalkyl, C1-C30 cycloalkyl, C1-C30 alkoxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl, substituted or unsubstituted C6-C60 aryloxy, halogen, substituted or unsubstituted C3-C30 heterocyclyl, cyano, mono-or di (C1-C30 alkyl) amino, mono-or di (substituted or unsubstituted C6-C60 aryl) amino, C1-C30 alkylthio, (substituted or unsubstituted C5-C60 heteroaryl) amino, C1-C30 alkylsilyl, (substituted or unsubstituted C6-C60 aryl) silyl, (substituted or unsubstituted C5-C60 heteroaryl) silyl, (substituted or unsubstituted C6-C60 aryl) oxy, (substituted or unsubstituted C5-C60 heteroaryl) oxy, or substituted or unsubstituted C5-C60 heteroaryl) oxy;

R ^a and R ^b Independently represent C3-C30 alkyl or C5-C30 cycloalkyl.

Further, the platinum (II) complex represented by Pt (I) or Pt (II) can be selected from the following structures:

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the present invention also provides a composition comprising one or more of the metal platinum (II) complexes described above and one or more host materials, wherein the host material is represented by formula (a) or formula (B):

wherein:

in the formula (A), X ¹ 、X ² And X ³ Each independently represents CH or N, and at least one of which is N;

Ar ¹ 、Ar ² and Ar ³ Each independently represents any one of a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C5-C60 heteroaryl group, a mono-or di (substituted or unsubstituted C6-C60 aryl) amino group, a di (substituted or unsubstituted C5-C60 heteroaryl) amine group, a 9- (di-substituted or unsubstituted C5-C60 heteroaryl) carbazolyl group, a C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C60 aryl) silyl group, a substituted or unsubstituted C5-C60 heteroaryl) silyl group, a substituted or unsubstituted C6-C60 aryl) oxysilyl group, or a (substituted or unsubstituted C5-C60 heteroaryl) oxysilyl group;

in formula (B), the dotted line indicates that the two aryl groups are not connected, or form a five to seven membered ring by single bonds and other linking atoms or groups;

R ^a1 、R ^b1 and R ^c1 Each independently represents any one of a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C5-C60 heteroaryl group, a mono-or di (substituted or unsubstituted C6-C60 aryl) amino group, a di (substituted or unsubstituted C5-C60 heteroaryl) amine group, a 9- (di-substituted or unsubstituted C5-C60 heteroaryl) carbazolyl group, a C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C60 aryl) silyl group, a substituted or unsubstituted C5-C60 heteroaryl) silyl group, a substituted or unsubstituted C6-C60 aryl) oxysilyl group, or a (substituted or unsubstituted C5-C60 heteroaryl) oxysilyl group.

The present invention also provides an organic light emitting device, comprising:

a first electrode;

a second electrode;

a light-emitting layer disposed between the first electrode and the second electrode, the light-emitting layer comprising the above composition.

Further, the light-emitting layer contains the metal platinum (II) complex.

Further, the light emitting layer contains a host material and a dopant material, the amount of the host material is larger than that of the dopant material, and the dopant material includes the platinum (II) complex represented by Pt- (I) or formula Pt- (II).

Further, the host material includes two different host materials.

Further, the dopant further comprises a metal platinum (II) complex and a fluorescent doping material.

Further, the host material includes an electron-transporting host material represented by formula (a) and a hole-transporting host material represented by formula (B):

wherein:

in the formula (A), X ¹ 、X ² And X ³ Each independently represents CH or N, and at least one further one of which is N; ar (Ar) ¹ 、Ar ² And Ar ³ Each independently represents any one of substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl, mono-or di (substituted or unsubstituted C6-C60 aryl) amino, di (substituted or unsubstituted C5-C60 heteroaryl) amino, 9- (di-substituted or unsubstituted C5-C60 heteroaryl) carbazolyl, C1-C30 alkylsilyl, (substituted or unsubstituted C6-C60 aryl) silyl, (substituted or unsubstituted C5-C60 heteroaryl) silyl, (substituted or unsubstituted C6-C60 aryl) oxysilyl, (substituted or unsubstituted C5-C60 heteroaryl) oxysilyl;

in formula (B), the dotted line indicates that the two aryl groups are not linked, or form a five to seven membered ring by single bonds and other linking atoms or groups; r ^a1 、R ^b1 And R ^c1 Each independently represents any one of substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl, mono-or di (substituted or unsubstituted C6-C60 aryl) amino, di (substituted or unsubstituted C5-C60 heteroaryl) amino, 9- (di-substituted or unsubstituted C5-C60 heteroaryl) carbazolyl, C1-C30 alkylsilyl, (substituted or unsubstituted C6-C60 aryl) silyl, (substituted or unsubstituted C5-C60 heteroaryl) silyl, (substituted or unsubstituted C6-C60 aryl) oxysilyl, (substituted or unsubstituted C5-C60 heteroaryl) oxysilyl;

the present invention also provides an organic light emitting device, comprising: a cathode, an anode and an organic layer, wherein the organic layer comprises a light-emitting layer, an electron transport layer, a hole transport layer, wherein the light-emitting layer comprises a composition comprising one or more of the above-described metal platinum (II) complexes and one or more host materials, wherein the host materials are represented by formula (a) or formula (B):

wherein:

in the formula (A), X ¹ 、X ² And X ³ Each independent earth surfaceIs represented by CH or N, and at least one of which is N;

Further, the electron transport host material is selected from any one of the following compounds ETH-1 to ETH-132:

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the hole-transporting host material is selected from any one of a compound HTH-1 to a compound HTH-147:

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further, wherein the fluorescent doping material includes a compound represented by formula (BN 1), formula (BN 2), or formula (BN 3):

wherein, X and X ¹ 、X ² 、X ³ 、X ⁴ And X ⁵ Each independently of the others being O, S, se or NR ³⁰⁰ ；

R ¹⁰ 、R ¹¹ 、R ¹² 、R ¹³ 、R ¹⁴ 、R ¹⁰⁰ 、R ¹⁰¹ 、R ¹⁰² 、R ¹⁰³ 、R ¹⁰⁴ 、R ²⁰⁰ 、R ²⁰¹ 、R ²⁰² 、R ²⁰³ 、R ²⁰⁴ And R ³⁰⁰ Each independently represents mono-, di-, tri-, tetra-, or unsubstituted;

R ¹⁰ 、R ¹¹ 、R ¹² 、R ¹³ 、R ¹⁴ 、R ¹⁰⁰ 、R ¹⁰¹ 、R ¹⁰² 、R ¹⁰³ 、R ¹⁰⁴ 、R ²⁰⁰ 、R ²⁰¹ 、R ²⁰² 、R ²⁰³ 、R ²⁰⁴ and R ³⁰⁰ Each independently represents any one of hydrogen, deuterium, a C1-C30 alkyl group, a C1-C30 haloalkyl group, a C1-C30 cycloalkyl group, a C1-C30 alkoxy group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C5-C60 heteroaryl group, a substituted or unsubstituted C6-C60 aryloxy group, halogen, a substituted or unsubstituted C3-C30 heterocyclic group, a cyano group, a mono-or di-C1-C30 alkyl amino group, a mono-or di-C6-C60 aryl) amino group, a C1-C30 alkylthio group, a substituted or unsubstituted (C5-C60 heteroaryl) amino group, a C1-C30 alkylsilyl group, a substituted or unsubstituted (C6-C60 aryl) silyl group, a substituted or unsubstituted (C5-C60 heteroaryl) oxy group, or a substituted or unsubstituted (C5-C60 heteroaryl) oxy group.

Further, the fluorescent doping material is one of a compound BN1-1 to a compound BN1-44, a compound BN2-1 to a compound BN2-96 or a compound BN3-1 to a compound BN 3-50:

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wherein: wherein Ph represents a phenyl group and D4 and D5 are meant to be substituted with 4 and 5 deuterium atoms, respectively.

The invention also provides application of the composition in manufacturing an organic light-emitting device.

The invention further provides a display or lighting device, which comprises the organic light-emitting device.

The Organic electroluminescent device of the present invention is any one of an Organic photovoltaic device, an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), electronic paper (e-paper), an Organic Photoreceptor (OPC), an Organic Thin Film Transistor (OTFT), an Organic Memory device (Organic Memory Element), a lighting device, and a display device.

In the present invention, the organic photoelectric device is an anode which can be formed by depositing a metal or an oxide having conductivity and an alloy thereof on a substrate by a sputtering method, electron beam evaporation, vacuum evaporation, or the like; and sequentially evaporating a hole injection layer, a hole transport layer, a luminescent layer, an air barrier layer and an electron transport layer on the surface of the prepared anode, and then evaporating a cathode. The organic electroluminescent device is prepared by vapor deposition of the cathode, the organic layer and the anode on the substrate except the above method. The organic layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer. In the invention, the organic layer is prepared by adopting a high polymer material according to a solvent engineering (spin-coating), tape-casting (tape-casting), doctor-blading (sector-Printing), screen-Printing (Screen-Printing), ink-jet Printing or Thermal-Imaging (Thermal-Imaging) method instead of an evaporation method, so that the number of the layers of the device can be reduced.

The materials used for the organic electroluminescent device according to the present invention may be classified as top emission, low emission, or double-sided emission. The compounds of the organic electroluminescent device according to the embodiment of the present invention can be applied to the aspects of organic solar cells, illuminating OLEDs, flexible OLEDs, organic photoreceptors, organic thin film transistors and other electroluminescent devices by a similar principle of the organic light emitting device.

The invention has the beneficial effects that: the excited state of the pyridocarbene-based tetradentate ring metalloplatinum (II) complex phosphorescent material has more metal-to-pyridocarbene charge transfer states due to the stronger electron withdrawing ability of the pyridocarbene compared with the benzocarbine platinum (II) complex (1) ³ MLCT) is beneficial to improving the radiation rate of the device, thereby prolonging the service life of the device. In addition, the host material provided by the invention has good chemical stability and thermal stability, and is easy to prepare an evaporation type OLED device, the host material composition can balance the transmission of holes and electrons, so that the energy transfer between a host and an object is more efficient, and the specific expression is that the current efficiency and the service life of an organic electroluminescent device manufactured by using the composition provided by the invention as a light-emitting layer are improved, and the lighting voltage is reduced. Further adopting a phosphorescence sensitized boron-containing compound system can improve the light color purity of the device.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts, wherein:

fig. 1 is a structural diagram of an organic electroluminescent diode device according to the present invention, in which 110 denotes a substrate, 120 denotes an anode, 130 denotes a hole injection layer, 140 denotes a hole transport layer, 150 denotes a light emitting layer, 160 denotes a hole blocking layer, 170 denotes an electron transport layer, 180 denotes an electron injection layer, and 190 denotes a cathode.

Detailed Description

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 of the present invention, 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 examples of combination molecules A-D are 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, mercapto, 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 in accordance with the atom substituted and the allowed valency 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 expressly stated to the contrary.

In defining various terms，“R ¹ ”、“R ² ”、“R ³ "and" R ⁴ "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, halo, 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, halo, hydroxy, nitro, silyl, sulfo-oxo, or thiol as described herein.

The term "polyalkylene group" as used herein refers to a group containing two or more CH ₂ Groups and are attached to other identical moieties. "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-OR ¹ Wherein R is ¹ Is 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-OR ¹ -OR ² OR-OR ¹ -(OR ² ) _a -OR ³ Wherein "a" is an integer of 1 to 200, and R ¹ 、R ² And R ³ Each 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 30 carbon atoms, the structural formula of which contains at least one carbon-carbon double bond. Asymmetric structures such as (R) ¹ R ² )C＝C(R ³ R ⁴ ) Intended to include both the E and Z isomers. This can be presumed in the structural formula of the present invention in which an asymmetric olefin is present, or it can be clearly 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, carboxyl, ester, halogen, hydroxy, carbonyl, 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, carboxyl, ester, halogen, hydroxyl, carbonyl, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol as described herein.

The term "alkynyl" as used herein is a hydrocarbon group having 2 to 30 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, carboxyl, ester, halogen, hydroxyl, carbonyl, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol 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, carboxyl, ester, halogen, hydroxyl, carbonyl, 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, phenyl, naphthyl, phenyl, biphenyl, phenoxyphenyl, anthracenyl, phenanthrenyl, 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 that does not contain heteroatoms. The aryl group may be substituted or unsubstituted. The aryl 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, carboxyl, ester, halogen, hydroxyl, carbonyl, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol 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 fused 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 an abbreviated form of carbonyl (i.e., C = O).

The term "amine" or "amino" as used herein is defined by the formula-NR ¹ R ² Is represented by the formula (I) in which R ¹ And R ² Can 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) ₂ Wherein 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) R ¹ OR-C (O) OR ¹ Is represented by the formula (I) in which R ¹ 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) ¹ O(O)C-R ² -C(O)O) _a -or- (R) ¹ O(O)C-R ² -OC(O)) _a -represents wherein R ¹ And R ² May 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 group produced by the reaction between a compound having at least two carboxyl groups and a compound having at least two hydroxyl groups.

The term "ether" as used herein is defined by the formula R ¹ OR ² Is represented by the formula (I) in which R ¹ And R ² May 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) ¹ O-R ² O) _a -represents wherein R ¹ And R ² May 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 of 3 to 30 carbon atoms, and "heteroaryl" as used herein refers to monocyclic and polycyclic aromatic ring systems of no more than 60 carbon atoms: wherein at least one of the ring members is not carbon. The term includes azetidinyl, dioxanyl, furyl, 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, triazinyl including 1,3, 5-triazinyl and 1,2, 4-triazinyl, triazolyl including 1,2, 3-triazolyl and 1,3, 4-triazolyl, 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 R ¹ C(O)R ² Is represented by the formula (I) in which R ¹ And R ² May 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-N ₃ And (4) showing.

The term "nitro" as used herein is of the formula-NO ₂ And (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-SiR ¹ R ² R ³ Is represented by the formula (I) in which R ¹ 、R ² And R ³ And 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) R ¹ 、-S(O) ² R ¹ 、-OS(O) ² R ¹ or-OS (O) ² OR ¹ Is represented by the formula (I) in which R ¹ May 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) ² R ¹ A thio-oxo group of the formula, wherein R ¹ Can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl. The term "sulfone" as used herein is defined by the formula R ¹ S(O) ₂ R ² Is represented by the formula (I) in which R ¹ And R ² May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein. The term "sulfoxide", as used herein, refers toA formula of R ¹ S(O)R ² Is represented by the formula (I) in which R ¹ And R ² May 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 invention ¹ ”、“R ² ”、“R ³ ”、“R ⁿ "(wherein n is an integer) may independently have one or more of the groups listed above. For example, if R ¹ Being 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 before) 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 term "fused ring" as used herein means that two adjacent substituents may be fused to form a six-membered aromatic ring, a heteroaromatic ring, such as a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a m-diazacyclo ring, etc., as well as a saturated six-or seven-membered carbocyclic or carbocyclic ring, etc.

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

it is understood to be equivalent to the following formula:

where n is typically an integer. Namely, R ⁿ Is 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 specification ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ And so on. In the specification, R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ Etc. are each applicable to the citation of R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ Etc., 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 light emitting layer of Organic Light Emitting Devices (OLEDs), and have received great attention in academic and industrial fields. Over the last decade, much effort has been made, resulting in profitable applications 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 issue. The choice of host material has proven to be very important for the stability of blue devices. However, the triplet excited state (T1) minimum energy of the blue light emitting material is very high, which means that the triplet excited state (T1) minimum 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 compounds or complex complexes comprising platinum. 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 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 phenylcarbazole-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.

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.

The disclosure may be understood more readily by reference to the following detailed description and the examples included therein.

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.

In a preferred embodiment of the present invention, the OLED device according to the invention comprises a hole transport layer, which may preferably be selected from known or unknown materials, particularly preferably from the following structures, without representing the present invention being limited to the following structures:

in a preferred embodiment of the present invention, the hole transport layer contained in the OLED device of the present invention comprises one or more p-type dopants. Preferred p-type dopants of the present invention are, but do not represent a limitation of the present invention to:

in a preferred embodiment of the present invention, the electron transport layer may be selected from at least one of the compounds ET-1 to ET-13, but does not represent that the present invention is limited to the following structures:

synthetic examples

The following examples of compound syntheses, compositions, 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 temperatures of ℃ or at ambient temperature and at pressures close to atmospheric 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.

¹ H NMR(500MHz)、 ¹ H NMR(400MHz)、 ¹³ C NMR (126 MHz) spectra were determined on an ANANCE III (500M) model NMR spectrometer; unless otherwise stated, nuclear magnetic resonance is carried out by using DMSO-d ₆ Or CDCl containing 0.1% of TMS ₃ As a solvent, wherein ¹ H NMR spectrum if CDCl ₃ As solvent, TMS (δ =0.00 ppm) was used as internal standard; with 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. ¹³ In the C NMR spectrum, as CDCl ₃ (delta =77.00 ppm) or DMSO-d ₆ (δ =39.52 ppm) as an internal standard. Measuring on an HPLC-MS Agilent 6210TOF LC/MS type mass spectrometer; HRMS spectra were determined on an Agilent 6210TOF LC/MS liquid chromatography-time of flight mass spectrometer. ¹ H NMR spectrum data: s = singlet, d = doubtet, t = triplet, q = quartz, p = quintet, m = multiplex, br = broad.

Synthetic route

Example 1: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt1 is as follows:

synthesis of intermediate (DtBu-NO 2) into a three-necked flask equipped with a magnetic stirrer were charged DtBu-Br (10g, 37.14mmol,1.0 equivalent), NH2-NO2 (6.20g, 44.57mmol,1.2 equivalent), palladium acetate (500mg, 1.86mmol,5 mol%), 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene (XantPhos) (2.15g, 3.71mmol, 10mol%) and cesium carbonate (24.20g, 74.29mmol,2.0 equivalent). The nitrogen was then purged three times and toluene (150 mL) was added under nitrogen. Reacting in an oil bath at 110 ℃ for 50 hours, cooling to room temperature, filtering, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =50, to give 6.47g of brown solid in 53% yield. The structure was not characterized and used directly in the next step.

Synthesis of intermediate (DtBu-NH 2) into a three-necked flask equipped with a magnetic stirrer were charged DtBu-NO2 (6.40g, 19.54mmol,1.0 eq), palladium on carbon (624 mg,0.29mmol,1.5 mmol), and ethanol (100 mL) and ethyl acetate (20 mL) were added. After 16 hours of reaction in a hydrogen atmosphere, the reaction mixture was filtered through celite, and the solvent was distilled off under reduced pressure to obtain 5.80g of a white solid with a yield of 99%. ¹ H NMR(500MHz,DMSO-d ₆ )δ1.23(s,18H),5.58(s,2H),6.52(dd,J＝7.5,5.0Hz,1H),6.71(d,J＝1.5Hz,2H),6.84(t,J＝1.5Hz,1H),7.03(s,1H),7.25(dd,J＝7.5,1.5Hz,1H),7.60(dd,J＝5.0,1.5Hz,1H)。

Synthesis of intermediate (NH 1) into a three-necked flask with a magnetic stirrer were added DtBu-NH2 (1.20g, 4.04mmol,1.0 equiv.), tBu-Cl (1.95g, 4.04mmol,1.0 equiv.), dibenzylideneacetone dipalladium (111mg, 0.12mmol, 3mol%), 2- (di-t-butylphosphine) biphenyl (John Phos) (72mg, 0.24mmol,6 mol%) and sodium t-butoxide (776mg, 8.07mmol,2.0 equiv.). The nitrogen was purged three times and toluene (25 mL) was added under nitrogen. Reacting in an oil bath at 110 ℃ for 36 hours, cooling to room temperature, filtering, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =50, 1-10, yielding 1.37g of a brown solid in 46% yield. The twoThe amine intermediate is easy to oxidize and partially deteriorate, so that the next reaction is influenced; therefore, the product can be directly used for the next reaction in order to reduce the deterioration of the product. ¹ H NMR(500MHz,DMSO-d ₆ )δ1.20(s,18H),1.23(s,9H),1.23(s,9H),6.65(t,J＝2.0Hz,1H),6.70(dd,J＝7.5,5.0Hz,1H),6.74(d,J＝1.5Hz,2H),6.86(t,J＝1.5Hz,1H),7.07(dd,J＝8.5,2.0Hz,1H),7.29–7.33(m,4H),7.38(dd,J＝7.5,1.5Hz,1H),7.39–7.43(m,2H),7.54(t,J＝2.0Hz,1H),7.58(dd,J＝2.0,0.5Hz,1H),7.67(dd,J＝5.0,1.5Hz,1H),7.73(dt,J＝8.5,1.0Hz,1H),8.03(s,1H),8.16–8.20(m,1H),8.22(d,J＝8.5Hz,1H),8.54(dd,J＝5.5,0.5Hz,1H)。

Synthesis of ligand L1 into a three-necked flask equipped with a magnetic stirrer were charged NH1 (1.10 g,1.48mmol,1.0 eq), ammonium hexafluorophosphate (482mg, 2.96mmol,2.0 eq), nitrogen was purged three times, and triethyl orthoformate (6 mL) was added under nitrogen protection. Reacting in an oil bath at 90 ℃ for 19 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating by a silica gel chromatographic column, and eluting: dichloro/ethyl acetate =100 to give 820mg of brown solid in 61% yield. The structure was not characterized and used directly in the next step.

Synthesis of Pt1 to a sealed tube with a magnetic stirrer, L1 (500mg, 0.56mmol,1.0 eq), (1, 5-cyclooctadiene) platinum dichloride (208mg, 0.56mmol,1.0 eq) and sodium acetate (137mg, 1.67mmol,3.0 eq) were added, nitrogen was purged three times, tetrahydrofuran (10 mL) was added under nitrogen protection, and oxygen was bubbled through with nitrogen for 30min. Reacting in an oil bath at 120 ℃ for 44 hours, cooling the reaction to room temperature, and then distilling under reduced pressure to remove the solvent, separating the obtained crude product by using a silica gel chromatographic column, eluting: petroleum ether/dichloromethane =2, 1-1, yielding 212mg of yellow solid in 40% yield. ¹ H NMR(500MHz,CDCl ₃ )δ1.19(s,9H),1.31(br,18H),1.51(s,9H),6.10(dd,J＝6.5,2.0Hz,1H),7.25(d,J＝2.0Hz,1H),7.30(dd,J＝8.0,5.0Hz,1H),7.32–7.38(m,2H),7.39(t,J＝2.0Hz,1H),7.46(d,J＝8.0Hz,1H),7.64(s,2H),7.70–7.74(m,2H),7.86(d,J＝8.0Hz,1H),7.93(d,J＝2.0Hz,1H),8.03–8.06(m,1H),8.60(dd,J＝5.0,1.5Hz,1H),8.68(d,J＝6.5Hz,1H),8.77(d,J＝2.0Hz,1H)。

Example 2: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt2 is as follows:

synthesis of intermediate (NH 2) into a three-necked flask with a magnetic stirrer were added DtBu-NH2 (2.09g, 7.03mmol,1.2 equiv.), H-Cl (2.50g, 5.86mmol,1.0 equiv.), dibenzylideneacetone dipalladium (161mg, 0.18mmol, 3mol%), 2- (di-tert-butylphosphino) biphenyl (John Phos) (209mg, 0.70mmol, 12mol%) and sodium tert-butoxide (1.13g, 11.72mmol,2.0 equiv.). The nitrogen was purged three times and toluene (35 mL) was added under nitrogen. Reacting in an oil bath at 120 ℃ for 54 hours, cooling to room temperature, filtering, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =50, to give 2.58g of brown solid in 64% yield. ¹ H NMR(500MHz,DMSO-d ₆ )δ1.20(s,18H),1.25(s,9H),6.61(ddd,J＝8.0,2.5,1.0Hz,1H),6.72–6.78(m,3H),6.86(t,J＝1.5Hz,1H),7.08(dd,J＝8.5,2.0Hz,1H),7.23(t,J＝8.0Hz,1H),7.27(d,J＝2.0Hz,1H),7.29–7.34(m,2H),7.38–7.44(m,3H),7.46(ddd,J＝8.5,2.0,1.0Hz,1H),7.56(t,J＝2.0Hz,1H),7.60(dd,J＝2.0,0.5Hz,1H),7.72–7.77(m,2H),8.08(s,1H),8.19(dt,J＝7.5,1.0Hz,1H),8.23(d,J＝8.5Hz,1H),8.56(dd,J＝5.5,0.5Hz,1H)。

Synthesis of ligand L2 to a three-necked flask with magnetic stirrer was added NH2 (2.40g, 3.49mmol,1.0 eq), ammonium hexafluorophosphate (1.71g, 10.47mmol,3.0 eq), nitrogen was purged three times and triethyl carbamate (10 mL) was added under nitrogen protection. Reacting in an oil bath at 70 ℃ for 36 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating by a silica gel chromatographic column, and eluting: dichloro/ethyl acetate =100, to give 2.48g of brown solid in 84% yield. ¹ H NMR(500MHz,DMSO-d ₆ )δ1.30(s,9H),1.37(s,18H),7.18(dd,J＝8.5,2.0Hz,1H),7.34(td,J＝7.5,1.0Hz,1H),7.42–7.48(m,3H),7.49(d,J＝2.0Hz,1H),7.66(d,J＝1.5Hz,2H),7.69(d,J＝1.0Hz,1H),7.72–7.81(m,5H),7.86(dd,J＝8.5,5.0Hz,1H),8.24(dt,J＝7.5,1.0Hz,1H),8.33(d,J＝8.5Hz,1H),8.47(dd,J＝8.5,1.5Hz,1H),8.59(dd,J＝5.5,0.5Hz,1H),8.83(dd,J＝5.0,1.5Hz,1H),10.77(s,1H)。

Synthesis of Pt2 to a sealed tube with a magnetic stirrer, L2 (2.48g, 2.94mmol,1.0 eq), (1, 5-cyclooctadiene) platinum dichloride (1.10 g,2.94mmol,1.0 eq) and sodium acetate (724mg, 8.82mmol,3.0 eq) were added, nitrogen was purged three times, tetrahydrofuran (40 mL) was added under nitrogen protection, and oxygen was bubbled with nitrogen for 30min. And (3) reacting in an oil bath kettle at 120 ℃ for 70 hours, cooling the reaction to room temperature, then distilling under reduced pressure to remove the solvent, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =2, 1-1, gave 917mg of yellow solid in 35% yield. ¹ H NMR(500MHz,CDCl ₃ )δ0.89(s,9H),1.21(br,18H),5.57(s,1H),7.03–7.12(m,2H),7.26–7.35(m,4H),7.45(d,J＝8.0Hz,1H),7.54(s,2H),7.59–7.64(m,3H),7.83(d,J＝8.0Hz,1H),7.97–8.01(m,1H),8.38(d,J＝6.5Hz,1H),8.61(dd,J＝5.0,1.5Hz,1H),8.70(d,J＝6.0Hz,1H)。

Example 3: the synthesis route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt4 is as follows:

synthesis of intermediate (NH 4) to a three-necked flask with a magnetic stirrer were added H-NH2 (6.55g, 16.07mmol,1.0 eq), diPr-Cl (5.57g, 19.29mmol,1.2 eq), dibenzylideneacetone dipalladium (221mg, 0.24mmol,1.5 mol%), 1 '-binaphthyl-2, 2' -bis-diphenylphosphine (BINAP) (600mg, 0.96mmol,6 mol%) and sodium t-butoxide (3.86g, 40.18mmol,2.5 eq). The nitrogen was purged three times and toluene (60 mL) was added under nitrogen. Reacting in an oil bath at 110 ℃ for 24 hours, cooling to room temperature, filtering, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =50, to give 9.91g of a brown solid in 93% yield. ¹ H NMR(500MHz,DMSO-d ₆ )δ1.00(d,J＝4.5Hz,6H),1.12(d,J＝4.5Hz,6H),1.25(s,9H),2.99–3.07(m,2H),6.08(dd,J＝7.5,1.5Hz,1H),6.54(dd,J＝7.5,5.0Hz,1H),6.64(ddd,J＝8.0,2.5,1.0Hz,1H),6.70(s,1H),7.12(dd,J＝8.5,2.0Hz,1H),7.22–7.33(m,6H),7.40–7.46(m,3H),7.54(ddd,J＝8.5,2.0,1.0Hz,1H),7.59(dd,J＝1.5,0.5Hz,1H),7.70(t,J＝2.0Hz,1H),7.77(dt,J＝8.5,1.0Hz,1H),8.19–8.21(m,2H),8.26(d,J＝8.5Hz,1H),8.57(dd,J＝5.5,0.5Hz,1H)。

Synthesis of ligand L4 into a three-necked flask with magnetic stirrer was added NH4 (9.90g, 15mmol,1.0 eq), ammonium hexafluorophosphate (7.34g, 45mmol,3.0 eq), nitrogen was purged three times, and triethyl orthoformate (15 mL) was added under nitrogen protection. And (3) reacting in an oil bath at 75 ℃ for 9 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating by using a silica gel chromatographic column, and eluting: dichloro/ethyl acetate =100, to give 8.24g of brown solid in 67% yield. ¹ H NMR(500MHz,DMSO-d ₆ )δ1.30(s,9H),1.37(s,18H),7.18(dd,J＝8.5,2.0Hz,1H),7.34(td,J＝7.5,1.0Hz,1H),7.41–7.48(m,3H),7.49(d,J＝2.0Hz,1H),7.66(d,J＝1.5Hz,2H),7.69(dd,J＝1.5,0.5Hz,1H),7.73–7.79(m,5H),7.86(dd,J＝8.5,5.0Hz,1H),8.24(dt,J＝7.5,1.0Hz,1H),8.33(d,J＝8.5Hz,1H),8.47(dd,J＝8.5,1.5Hz,1H),8.59(dd,J＝5.5,0.5Hz,1H),8.83(dd,J＝5.0,1.5Hz,1H),10.77(s,1H)。

Synthesis of Pt4 to a sealed tube with a magnetic stirrer, L4 (3.70g, 4.54mmol,1.0 eq), (1, 5-cyclooctadiene) platinum dichloride (1.70g, 4.54mmol,1.0 eq) and sodium acetate (1.12g, 13.62mmol,3.0 eq) were added, nitrogen was purged three times, tetrahydrofuran (60 mL) was added under nitrogen protection, and oxygen was bubbled with nitrogen for 30min. And (3) reacting for 65 hours in an oil bath kettle at the temperature of 120 ℃, cooling the reaction to room temperature, then distilling under reduced pressure to remove the solvent, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =2, 1-1, to give 1.57g of yellow solid, yield 40%. ¹ H NMR(500MHz,CDCl ₃ )δ0.90(br,6H),1.14(br,6H),1.26(s,9H),3.07(br,2H),6.04(dd,J＝6.0,2.0Hz,1H),7.21–7.29(m,5H),7.32(td,J＝7.5,1.0Hz,1H),7.35–7.46(m,4H),7.73–7.79(m,2H),7.96(d,J＝2.0Hz,1H),7.99–8.01(m,1H),8.55–8.58(m,2H),8.62(d,J＝6.5Hz,1H)。

Example 4: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt5 is as follows:

synthesis of intermediate NH5 the intermediate H-NH2 was replaced by H-NH2-D4 according to the similar synthesis procedure and reaction conditions as for intermediate NH4 in example 3, and the target product NH5 was synthesized in a yield of 92% as a brown solid (1.93 g). Since it is easily oxidized and not stable enough, it is directly used in the next reaction.

Synthesis of ligand L5 according to the similar synthetic procedures and reaction conditions of ligand L4 in example 3, the target product L5 was synthesized as a brown solid in an amount of 1.26g with a yield of 64%. And (2) MS: theoretical molecular weight [ M] ⁺ 674.4; measured molecular weight [ M] ⁺ :674.2。

Synthesis of Pt5 according to the similar synthetic procedure and reaction conditions of the metal complex Pt4 in example 3, the target product Pt5 was synthesized as a yellow solid 787mg with a yield of 41%. Theoretical molecular weight [ M + H] ⁺ 867.3; molecular weight [ M + H ] was measured] ⁺ :867.4。

Example 5: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt18 is as follows:

synthesis of intermediate NH18 according to the similar synthesis steps and reaction conditions of intermediate NH4 in example 3, intermediate H-NH2 was replaced by tBu-NH2-D4 to obtain the target product NH18 in a yield of 94% as a brown solid, 1.68 g. Directly used for the next reaction.

Synthesis of ligand L18 according to the similar synthetic procedures and reaction conditions of ligand L4 in example 3, the target product L18 was synthesized in a yield of 68% as a brown solid, 1.01 g. Theoretical molecular weight [ M] ⁺ 730.4; measured molecular weight [ M] ⁺ :730.5。

Synthesis of Pt18 according to the similar synthesis procedure and reaction conditions of the metal complex Pt4 in example 3, the target product Pt18 is synthesized, 584mg of yellow solid is obtained, and the yield is 38%. Theoretical molecular weight [ M + H] ⁺ 923.4; molecular weight [ M + H ] was measured] ⁺ :923.3。

Example 6: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt19 is as follows:

synthesis of intermediate NH19 the intermediate H-NH2 was replaced with Si-NH2-D4 according to the similar synthesis procedure and reaction conditions as for intermediate NH4 in example 3 to give the target product NH19 as a brown solid in 1.52g with a yield of 86%. Directly used for the next reaction.

Synthesis of ligand L19 according to the similar Synthesis procedures and reaction conditions to those of ligand L4 in example 3, the objective product L19 was synthesized as a brown solid in an amount of 861mg with a yield of 58%. Theoretical molecular weight [ M] ⁺ 932.5; measured molecular weight [ M] ⁺ :932.5。

Synthesis of Pt19 according to the similar synthesis procedure and reaction conditions of the metal complex Pt4 in example 3, the target product Pt19 is synthesized to be 486mg of yellow solid with the yield of 32%. Theoretical molecular weight [ M + H] ⁺ 1125.4; molecular weight [ M + H ] was measured] ⁺ :1125.3。

Example 7: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt8 is as follows:

synthesis of intermediate NH8 according to the similar synthesis steps and reaction conditions of intermediate NH4 in example 3, intermediate H-NH2 was replaced with DiPr-NH2-D4 to synthesize the target product NH8, 1.26g of brown solid, yield 95%. Directly used for the next reaction.

Synthesis of ligand L8 according to the similar synthetic procedures and reaction conditions of ligand L4 in example 3, the target product L8 was synthesized in 756mg as a brown solid with a yield of 71%. Theoretical molecular weight [ M] ⁺ 834.5; measured molecular weight [ M] ⁺ :834.4。

Synthesis of Pt8 according to the similar synthesis procedure and reaction conditions of the metal complex Pt4 in example 3, the target product Pt8 was synthesized as a yellow solid in an amount of 453mg with a yield of 34%. Theoretical molecular weight [ M + H] ⁺ 1027.5; molecular weight [ M + H ] was measured] ⁺ :1027.6。

Example 8: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt22 is as follows:

synthesis of intermediate NH22 the intermediate H-Cl was replaced by H-Cl-D4 according to the similar synthesis procedure and reaction conditions as for intermediate NH2 in example 2 to give the desired product NH22 as a brown solid in 1.59g with a yield of 68%. Directly used for the next reaction.

Synthesis of ligand L22 according to the similar synthetic procedures and reaction conditions of ligand L2 in example 2, the desired product L22 was synthesized as a brown solid in an yield of 872mg (87%). Theoretical molecular weight [ M] ⁺ 702.4; measured molecular weight [ M] ⁺ :702.2。

Synthesis of Pt22 according to the similar synthesis procedure and reaction conditions of the metal complex Pt2 in example 2, the target product Pt22 was synthesized as a yellow solid in an amount of 623mg with a yield of 36%. Theoretical molecular weight [ M + H] ⁺ 895.4; measured molecular weight [ M + H] ⁺ :895.3。

Example 9: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt111 is as follows:

synthesis of intermediate NH111 according to the similar synthesis steps and reaction conditions of intermediate NH2 in example 2, intermediate DtBu-NH2 was replaced by Me-DtBu-NH2 and intermediate H-Cl was replaced by H-Cl-D6 to obtain the target product NH111 in a yield of 1.31g as a brown solid. Directly used for the next reaction.

Synthesis of ligand L111 according to the examplesThe synthesis procedure and reaction conditions similar to those of ligand L2 in example 2 gave target product L111 in a yield of 85% as a brown solid of 778 mg. Theoretical molecular weight [ M] ⁺ 718.4; measured molecular weight [ M] ⁺ :718.3。

Synthesis of Pt111 according to the similar synthesis procedure and reaction conditions of the metal complex Pt2 in example 2, the target product Pt111 was synthesized as a yellow solid 513mg with a yield of 35%. Theoretical molecular weight [ M + H] ⁺ 911.4; molecular weight [ M + H ] was measured] ⁺ :911.5。

Example 10: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt29 is as follows:

synthesis of intermediate NH29 the intermediate H-Cl was replaced with DiPr-Cl-D4 according to the procedures and conditions similar to those of intermediate NH2 in example 2, and the target product NH29 was synthesized in a yield of 67% as a brown solid, 1.51 g. Directly used for the next reaction.

Synthesis of ligand L29 according to the similar synthetic procedure and reaction conditions to ligand L2 in example 2, the desired product L29 was synthesized as a brown solid 803mg in 67% yield. Theoretical molecular weight [ M] ⁺ 904.6; measured molecular weight [ M] ⁺ :904.83。

Synthesis of Pt29 according to the similar synthesis procedure and reaction conditions of the metal complex Pt2 in example 2, the target product Pt29 is synthesized to be 327mg of yellow solid with a yield of 30%. Theoretical molecular weight [ M + H] ⁺ 1097.5; molecular weight [ M + H ] was measured] ⁺ :1097.4。

Example 11: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt49 is as follows:

synthesis of intermediate NH49 according to the similar synthesis steps and reaction conditions of intermediate NH2 in example 2, intermediate DtBu-NH2 is replaced by Me-DtBu-NH2, intermediate H-Cl is replaced by DiPr-Cl-D4-tBu, and the target product NH49 is synthesized with 1.21g of brown solid and yield of 75%. Directly used for the next reaction.

Synthesis of ligand L49 according to the similar synthetic procedure and reaction conditions of ligand L2 in example 2, the desired product L49 was synthesized as a brown solid 811mg with a yield of 61%. Theoretical molecular weight [ M] ⁺ 876.6; measured molecular weight [ M] ⁺ :876.5。

Synthesis of Pt49 according to the similar synthesis procedure and reaction conditions of the metal complex Pt2 in example 2, the target product Pt49 was synthesized as a yellow solid with a yield of 325mg of 31%. Theoretical molecular weight [ M + H] ⁺ 1069.5; molecular weight [ M + H ] was measured] ⁺ :1069.3。

Example 12: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt124 is as follows:

synthesis of intermediate NH124 according to the similar synthesis steps and reaction conditions of intermediate NH2 in example 2, intermediate DtBu-NH2 was replaced by tBu-DtBu-NH2, intermediate H-Cl was replaced by DiPr-Cl-D6-tBu, and the target product NH124 was synthesized with a brown solid of 1.29g and a yield of 77%. Directly used for the next reaction.

Synthesis of ligand L124 according to the similar Synthesis procedures and reaction conditions of ligand L2 in example 2, the target product L124 was synthesized as a brown solid (801 mg, yield 63%). Theoretical molecular weight [ M] ⁺ 920.6, and adding a catalyst; measured molecular weight [ M] ⁺ :920.8。

Synthesis of Pt124 according to the similar synthesis steps and reaction conditions of the metal complex Pt2 in example 2, the target product Pt124 is synthesized, 319mg of yellow solid is obtained, and the yield is 30%. Theoretical molecular weight [ M + H] ⁺ 1113.6; measured molecular weight [ M + H] ⁺ :1113.5。

Example 13: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt37 is as follows:

synthesis of intermediate NH37 the intermediate H-Cl was replaced with tBu-Cl-D4-D2 according to the procedures and reaction conditions similar to those of intermediate NH2 in example 2 to give the desired product NH37 as a brown solid in 1.59g with a yield of 77%. Directly used for the next reaction.

Synthesis of ligand L37 according to the similar synthetic procedures and reaction conditions of ligand L2 in example 2, the target product L37 was synthesized as a brown solid with a yield of 57 mg. Theoretical molecular weight [ M] ⁺ 774.5; measured molecular weight [ M] ⁺ :774.5。

Synthesis of Pt37 according to the similar synthesis procedure and reaction conditions of the metal complex Pt2 in example 2, the target product Pt37 was synthesized in 313mg as a yellow solid with a yield of 35%. Theoretical molecular weight [ M + H] ⁺ 967.5; molecular weight [ M + H ] was measured] ⁺ :967.6。

Example 14: the synthesis route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt44 is as follows:

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synthesis of intermediate NH44 according to the similar synthesis steps and reaction conditions of intermediate NH4 in example 3, intermediate H-NH2 was replaced with DiPr-NH2-D4-D2 to synthesize the target product NH44, 1.29g of brown solid, yield 85%. Directly used for the next reaction.

Synthesis of ligand L44 according to the similar synthetic procedures and reaction conditions of ligand L4 in example 3, the target product L44 was synthesized as 659mg of brown solid with a yield of 57%. Theoretical molecular weight [ M] ⁺ 850.5; measured molecular weight [ M] ⁺ :850.4。

Synthesis of Pt44 according to the similar synthesis procedure and reaction conditions of the metal complex Pt4 in example 3, the target product Pt44 was synthesized as a yellow solid of 356mg with a yield of 29%. Theoretical molecular weight [ M + H] ⁺ 1043.5; molecular weight [ M + H ] was measured] ⁺ :1043.4。

Example 15: the synthetic route of the tetradentate ring metal platinum (II) complex phosphorescent luminescent material Pt43 is as follows:

synthesis of intermediate NH43 the intermediate H-NH2 was replaced with tBu-NH2-D4-D2 according to the similar synthesis procedure and reaction conditions of intermediate NH4 in example 3 to give the desired product NH43 as a brown solid in 1.31g with 87% yield. Directly used for the next reaction.

Synthesis of ligand L43 according to the similar synthetic procedures and reaction conditions of ligand L4 in example 3, the target product L43 was synthesized as a brown solid (602 mg) with a yield of 58%. Theoretical molecular weight [ M] ⁺ 746.5; measured molecular weight [ M] ⁺ :746.4。

Synthesis of Pt43 according to the similar synthetic procedure and reaction conditions of the metal complex Pt4 in example 3, the target product Pt43 was synthesized as a yellow solid 337mg with a yield of 27%. Theoretical molecular weight [ M + H] ⁺ 939.4; molecular weight [ M + H ] was measured] ⁺ :939.5。

Description of theoretical calculation

Optimization of ground state (S) using Density Functional Theory (DFT) ₀ ) The geometry of the molecule. DFT calculations were performed using the B3LYP functional, with C, H, O, and N atoms using the 6-31G (d) group and Pt atoms using the LANL2DZ group.

Table 1: front line orbital energy level of partial metal complex

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According to the above calculation data, the materials all have large energy gaps (> 3.20 eV), and can meet the requirements of blue light materials; in addition, it is understood from the table that the front orbital levels (HOMO and LUMO) of the platinum (II) complex can be adjusted by controlling the ligand structure.

Importantly, the LUMO of the above-described pyridocarbene platinum (II) complex is mostly in the pyridocarbene moiety, compared to the LUMO of the control benzocarbene platinum (II) complex R1, which is mostly in the pyridine moiety, the excited state of the material has more metal-to-pyridocarbene charge transfer state (II) (( ³ MLCT) component; and because of both coordination bonds and feedback pi bonds between the carbene and the platinum (II), the stability of the carbene is higher than that of the carbene and the platinum (II); the above results are beneficial to improving the radiation rate of the semiconductor device, and further prolonging the service life of the device.

The host material involved in the present invention is obtained by a known synthesis method.

Preparing an OLED device: a P-doped material P-1 to P-5 is vapor-deposited on the surface or anode of an ITO glass having a light emitting area of 2mm x 2mm or the P-doped material is co-vapor-deposited with a compound shown in the table at a concentration of 1% to 50% to form a Hole Injection Layer (HIL) of 5 to 100nm and a Hole Transport Layer (HTL) of 5 to 200nm, and then a light emitting layer (EML) (which may contain the compound) of 10to 100nm is formed on the hole transport layer, and finally an Electron Transport Layer (ETL) of 20 to 200nm and a cathode of 50 to 200nm are sequentially formed using the compound, and if necessary, an Electron Blocking Layer (EBL) is added between the HTL and the EML, and an Electron Injection Layer (EIL) is added between the ETL and the cathode, thereby manufacturing an organic light emitting device. The OLEDs were tested by standard methods.

Comparing the device structure: ITO/P-4 (10 nm)/NPD (60 nm)/TAPC (10 nm)/2, 6-mCPy: platinum (II) complex (25 nm) (2, 6-mCPy: platinum (II) complex mass ratio is 90)/2, 6-mCPy (10 nm)/ET-14 (40 nm)/LiQ (1 nm)/Al (100 nm), wherein P-4 is TCHAN, and ET-14 is BPyTP.

The device structure (device structure 1) of the present application is selected from: ITO/P-4 (10 nm)/NPD (60 nm)/HTH-85 (5 nm)/platinum (II) complex HTH-85 (25 nm) (platinum (II) complex HTH-85 mass ratio of 10.

The device structure (device structure 2) of the present application is selected from: ITO/P-4 (10 nm)/NPD (60 nm)/HTH-85 (5 nm)/platinum (II) complex: HTH-85 (25 nm) (platinum (II) complex: boron-containing compound: HTH-85 at a mass ratio of 10.

TABLE 2

TABLE 3

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The thermal stability test shows that the introduction of a large-steric-hindrance alkyl group, such as a tert-butyl group, in the para-position of pyridine, wherein the alkyl group has five to 7 carbons, can obviously improve the thermal stability of the platinum (II) complex; the introduction of the bulky steric hindrance alkyl or substituted aryl on the benzene ring at the lower left of the molecule can also contribute to the improvement of the thermal stability.

As can be seen from table 2, device example 1 using the compound combination provided by the present invention as a host (two host materials) has a significant improvement in current efficiency and device lifetime while reducing the driving voltage, compared to device example R1 using the conventional host material 2, 6-mCPy.

As can be seen from table 3, the molecular structure of the platinum (II) complex material has a significant effect on the device performance, and introduction of alkyl group with large steric hindrance, alkyl group with large steric hindrance on the benzene ring or substituted aryl group at the para-position of pyridine and introduction of deuteration significantly improve the current efficiency and the device lifetime, as in device examples 1 to 15. The device performance of the device using the platinum (II) complex as the sensitizer and the boron-containing compound as the luminescent material is also significantly improved, as in device examples 16, 17 and 18.

In both tables 2 and 3, the deep blue devices have CIEy values less than 0.20. In addition, experiments show that the luminescent color purity of the device can be further improved by adding the boron-containing compound and adopting a sensitized device structure.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims

1. A metal platinum (II) complex has a structural formula shown as formula Pt- (I) or formula Pt- (II):

wherein:

R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ and R ⁶ Each independently represents any one of hydrogen, deuterium, a C1-C30 alkyl group, a C1-C30 haloalkyl group, a C1-C30 cycloalkyl group, a C1-C30 alkoxy group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C5-C60 heteroaryl group, a substituted or unsubstituted C6-C60 aryloxy group, halogen, a substituted or unsubstituted C3-C30 heterocyclic group, a cyano group, a mono-or di-C1-C30 alkyl amino group, a mono-or di-substituted or unsubstituted C6-C60 aryl) amino group, a C1-C30 alkylthio group, a substituted or unsubstituted C5-C60 heteroaryl) amino group, a C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C60 aryl) silyl group, a substituted or unsubstituted C5-C60 heteroaryl) oxy group, or a (substituted or unsubstituted C5-C60 heteroaryl) oxy group;

R ^a and R ^b Each independently represents a C3-C30 alkyl group or a C5-C30 cycloalkyl group.

2. The metal platinum (II) complex of claim 1 selected from one or more of the following structures:

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3. a composition comprising one or more platinum (II) complexes of any one of claims 1-2 and one or more host materials, wherein the host material is represented by formula (a) or formula (B):

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wherein:

Ar ¹ 、Ar ² and Ar ³ Each independently represents any one of a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C5-C60 heteroaryl group, a mono-or di- (substituted or unsubstituted C6-C60 aryl) amino group, a di- (substituted or unsubstituted C5-C60 heteroaryl) amine group, a 9- (di-substituted or unsubstituted C5-C60 heteroaryl) carbazolyl group, a C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C60 aryl) silyl group, a substituted or unsubstituted C5-C60 heteroaryl) silyl group, a substituted or unsubstituted C6-C60 aryl) oxysilyl group, or a (substituted or unsubstituted C5-C60 heteroaryl) oxysilyl group;

in formula (B), the dotted line indicates that the two aryl groups are not linked, or form a five to seven membered ring by single bonds and other linking atoms or groups;

4. An organic light emitting device comprising:

a first electrode;

a second electrode;

a light emitting layer disposed between the first electrode and the second electrode, wherein the light emitting layer comprises the composition of claim 3.

5. The organic light emitting device of claim 4, wherein the light emitting layer comprises a host material and a dopant material, the amount of the host material being greater than the amount of the dopant material.

6. The organic light emitting device of claim 5, wherein the dopant material further comprises a platinum (II) metal complex and a fluorescent dopant material.

7. An organic light emitting device, comprising: a cathode, an anode, and an organic layer, wherein the organic layer comprises a light emitting layer, an electron transport layer, a hole transport layer, wherein the light emitting layer comprises a composition comprising one or more platinum (II) complexes as claimed in any one of claims 1 to 2 and one or more host materials, wherein the host material is represented by formula (a) or formula (B):

wherein:

Ar ¹ 、Ar ² and Ar ³ Each independently represents a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C5-C60 heteroaryl group, a mono-or di (substituted or unsubstituted C6-C60 aryl) amino group, a di (substituted or unsubstituted C5-C60 heteroaryl) amino group, a 9- (di-substituted or unsubstituted C5-C60 heteroaryl) carbo groupAny of an oxazolyl group, a C1-C30 alkylsilyl group, a (substituted or unsubstituted C6-C60 aryl) silyl group, a (substituted or unsubstituted C5-C60 heteroaryl) silyl group, a (substituted or unsubstituted C6-C60 aryl) oxysilyl group, or a (substituted or unsubstituted C5-C60 heteroaryl) oxysilyl group;

8. An organic light-emitting device according to claim 7, the electron-transporting host material being selected from any one of the following compounds ETH-1 to ETH-132:

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9. the organic light-emitting device according to claim 7, the hole-transporting host material being selected from any one of compounds HTH-1 to HTH-147:

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10. the organic light emitting device of claim 6, wherein the fluorescent doping material is represented by formula BN1, formula BN2, or formula BN 3:

11. The organic light emitting device of claim 10, wherein the fluorescent dopant material is selected from one or more of the following compounds:

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wherein Ph represents a phenyl group and D4 and D5 mean substitution by 4 and 5 deuterium atoms, respectively.

12. Use of the composition according to claim 3 for the manufacture of an organic light emitting device.

13. An apparatus comprising the organic light emitting device according to claim 7.