Luminescent materials of tetradentate cyclometallated platinum(II) and palladium(II) complexes containing quinoline structural units and their uses

Abstract

The present invention provides tetradentate cyclometallated platinum(II) and palladium(II) complex luminescent materials containing quinoline structural units and uses thereof. [Solution] The present invention relates to the technical field of organic light-emitting materials, and provides platinum(II) and palladium(II) complex light-emitting materials containing the following quinoline structural unit: Compared with bidentate platinum complexes, the tetradentate-based cyclometallated platinum(II) and palladium(II) complexes provided by the present invention have high molecular rigidity, which can effectively suppress non-radiative transitions caused by molecular vibration and greatly improve quantum efficiency, and are expected to be widely used in various fields such as OLED displays and lighting.

Description

[Technical field]

[0001] The present invention relates to the technical field of metal-organic luminescent materials, in particular to tetradentate cyclometallated platinum(II) and palladium(II) complex luminescent materials containing quinoline structural units and uses thereof. [Background technology]

[0002] Organic Light-Emitting Diode (OLED) is a next-generation full-color display and lighting technology. OLED is an autonomous light-emitting device that does not require backlighting, is energy-saving, has low driving voltage, fast response speed, high resolution and contrast, wide viewing angle, and wide operating temperature range. It can also be used as a substrate on inexpensive glass, or flexible display components can be manufactured on flexible plastic substrates. It also has the advantages of low cost, simple manufacturing process, and large area manufacturing. Therefore, OLED is expected to be widely and hugely applied in high-end electronic products and aerospace fields. It also has a huge potential market in the field of flat solid-state lighting.

[0003] The core of the OLED field is the design and development of luminescent materials. In the early days, the luminescent materials in OLED devices were mainly organic small molecule fluorescent materials. However, as spin statistical quantum theory shows, in the state of electroluminescence, the ratio of singlet excitons to triplet excitons is 1:3, so traditional fluorescent materials can only utilize excitons in the singlet excited state, and their theoretical internal quantum efficiency is only 25%. In 1998, Professor Forrest of Princeton University and Professor Thompson of the University of Southern California discovered the phosphorescent electroluminescence phenomenon of heavy metal organic complex molecules at room temperature. Due to the strong spin-orbit interaction of heavy metal atoms, this type of complex can effectively promote the intersystem crossing (ISC) of excitons from singlet to triplet. This allows OLED devices to fully utilize all singlet and triplet excitons generated by electrical excitation, and the theoretical internal quantum efficiency of luminescent materials can reach 100% (Non-Patent Document 1). Thus, the development of OLED luminescent materials has entered a new era.

[0004] At present, the heavy metal phosphorescent organic complex molecules suitable for commercial application are basically all cyclometallated iridium(III) complexes, and the number is limited. The content of platinum element in the earth's crust and the annual production amount in the world are both about 10 times that of iridium element. IrCl used for the production of iridium(III) complex phosphorescent materials 3 H 2 The price of PtCl O (1100 RMB / g) is also high for the production of platinum(II) complex phosphorescent materials. 2 (210 RMB / g). In addition, the production of iridium(III) complex phosphorescent materials involves four-step reactions, including iridium(III) dimerization, iridium(III) intermediate ligand exchange, synthesis of mer-iridium(III) complex and isomer conversion of mer- to fac-iridium(III) complex, which greatly reduces the overall yield and the raw material IrCl 3 H 2The utilization rate of O has been greatly reduced, which has pushed up the production cost of iridium (III) complex phosphorescent materials. In comparison, the production of platinum (II) complex phosphorescent materials only requires the reaction design of platinum salt in the final ligand metallization reaction, which has a high utilization rate of platinum element and can further reduce the production cost of platinum (II) complex phosphorescent materials. In other words, the production cost of platinum (II) complex phosphorescent materials is much lower than that of iridium (III) complex phosphorescent materials.

[0005] Bidentate-based cyclometalated platinum(II) complexes have low molecular rigidity, and are prone to twisting into two bidentate ligands and non-radiative decay due to vibration, which reduces the quantum efficiency of phosphorescence. Meanwhile, tridentate-based cyclometalated platinum(II) complexes require a second coordinated anion (such as an anion of alkyne, Cl-, carbene, etc.), which reduces the chemical and thermal stability of the complex. All of the above reasons are disadvantageous for use as phosphorescent materials in OLED devices. In comparison, tetradentate-based cyclometalated platinum(II) complexes have high molecular rigidity, high radiative emission rate, and greatly improved quantum efficiency, while at the same time having high chemical and thermal stability, making them ideal molecules for the evolution of new OLED phosphorescent materials. The development of new stable and highly efficient phosphorescent light-emitting materials is of great significance, as it will determine the development of the OLED industry. [Prior art documents] [Non-patent literature]

[0006] [Non-Patent Document 1] Nature, 1998, 395, 151 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention relates to the technical field of metal-organic light-emitting materials, in particular platinum(II) and palladium(II) complexes containing quinoline structural units. Complexes of this type can be used as light-emitting materials in OLED devices. [Means for solving the problem]

[0008] In a first aspect, an embodiment of the present invention provides platinum(II) and palladium(II) complexes containing quinoline structural units, the platinum(II) and palladium(II) complexes containing quinoline structural units having a structure represented by general formula (I):

[0009] [ka]

[0010] During the ceremony, M is selected from Pt or Pd; A is O, S or NR 6 is selected from X is O, S, CH 2 , C.H.D., C.D. 2 , C.R. 7 R 8 , C=O, SiR 9 R 10 , N.H., N.D., N.R. 11 , P.H., P.D., P.R. 12 , R 13 P=O, S=O, or SO 2 Well, X is O, S or NR 14 is selected from Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Y 13 and Y 14 are each independently N or CH; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 each independently represents a mono-, di-, tri-, tetra- or unsubstituted group; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 each independently represents hydrogen, deuterium, an alkyl group, a halogenated alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, a heteroaryl group, an aryloxy group, a halogen, a cycloalkenyl group, a heterocyclyl group, an alkenyl group, an alkynyl group, a 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 ester group, a nitrile group, an isonitrile group, an alkoxycarbonyl group, an acylamino 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 phosphoramide group, an imino group, a sulfo group, a carboxyl group, a hydrazino group, a silyl group, a substituted silyl group, a polymerizable group, or a combination thereof, and two or more adjacent R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 can optionally be connected to form a fused ring.

[0011] Furthermore, the platinum(II) and palladium(II) complexes containing the above-mentioned quinoline structural unit are characterized in that the above-mentioned platinum complexes have a structure represented by general formula (II), (III), (IV) or (V).

[0012] [ka]

[0013] [ka]

[0014] [ka]

[0015] [ka]

[0016] Furthermore, platinum(II) and palladium(II) complexes containing the above-mentioned quinoline structural unit are shown below on the left: [ka] is preferably any one selected from the following structures:

[0017] [ka]

[0018] Furthermore, the platinum(II) and palladium(II) complexes containing the above-mentioned quinoline structural unit are characterized in that the above-mentioned platinum and palladium(II) complexes have any one of the following structures:

[0019] [ka]

[0020] [Chemistry]

[0021] [Chemistry]

[0022] [Chemistry]

[0023] [Chemistry]

[0024] [Chemistry]

[0025] [Chemistry]

[0026] [Chemistry]

[0027] [Chemistry]

[0028] [Chemistry]

[0029] [Chemistry]

[0030] [Chemistry]

[0031] [ka]

[0032] [ka]

[0033] In the present invention, the platinum(II) and palladium(II) complexes containing quinoline structural units are used as light-emitting materials and can be used in electroluminescent devices. They can also be used in full-color displays, light-emitting displays, or organic light-emitting diodes. Here, the device includes at least one cathode, at least one anode, and at least one light-emitting layer, and at least one of the light-emitting layers includes any of the platinum(II) and palladium(II) complexes containing the quinoline structural units described above. Effect of the Invention

[0034] The beneficial effects of the present invention are as follows: Compared with bidentate platinum complexes, the tetradentate-based cyclometalated platinum(II) complexes of the present invention have high molecular rigidity, which can effectively suppress non-radiative transitions caused by molecular vibration, and greatly improve the quantum efficiency. At the same time, the tetradentate ligand is also advantageous for enhancing the chemical stability and thermal stability of the material molecule. The present invention adjusts the photophysical properties of platinum complexes by changing the ligand structure surrounding the metal center and controlling the substituent structure on the ligand. It can be widely applied in various fields such as OLED displays and lighting. [Brief description of the drawings]

[0035] To more clearly explain the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings that need to be used in the description of the embodiments. However, the drawings in the following description are only some embodiments of the present invention, and it is obvious that those skilled in the art can obtain other drawings based on these drawings without creative labor.

[0036] [Figure 1] It is the emission spectrum at room temperature in a methylene chloride solution of the platinum complex Pt1 in a specific embodiment. [Diagram 2] It is the emission spectrum at room temperature in a methylene chloride solution of the platinum complex Pt2 in a specific embodiment. [Diagram 3] It is the emission spectrum at room temperature in a methylene chloride solution of the platinum complex Pt3 in a specific embodiment. [Figure 4] It is the emission spectrum at room temperature in a methylene chloride solution of the platinum complex Pt42 in a specific embodiment. [Diagram 5] It is a comparison of the distributions of the HOMO and LUMO orbits and their energy levels of Pt1, Pt2, Pt3, and Pt4 obtained by calculation using density functional theory (DFT). [Figure 6] It is a comparison of the distributions of the HOMO and LUMO orbits and their energy levels of Pt5, Pt6, Pt7, and Pt8 obtained by calculation using density functional theory (DFT). [Figure 7] It is a comparison of the distributions of the HOMO and LUMO orbits and their energy levels of Pt9, Pt10, Pt11, and Pt12 obtained by calculation using density functional theory (DFT). [Figure 8] It is a comparison of the distributions of the HOMO and LUMO orbits and their energy levels of Pt13, Pt14, Pt15, and Pt16 obtained by calculation using density functional theory (DFT). [Figure 9] It is a comparison of the distributions of the HOMO and LUMO orbits and their energy levels of Pt17, Pt18, Pt19, and Pt20 obtained by calculation using density functional theory (DFT). [Figure 10]This is a comparison of the distribution of HOMO and LUMO orbitals and their energy levels for Pt21, Pt22, Pt23, and Pt24 calculated using density functional theory (DFT). [Figure 11] This is a comparison of the distribution of HOMO and LUMO orbitals and their energy levels of Pt397, Pt398, Pt399, and Pd1 calculated using density functional theory (DFT). [Figure 12] This is a comparison of the distribution of HOMO and LUMO orbitals and their energy levels of Pd2, Pd3, Pd4, and Pd5 calculated using density functional theory (DFT). [Figure 13] FIG. 1 is a conceptual diagram of the structure of an organic light-emitting element.

[0037] It should be noted that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0038] The present disclosure may be more readily understood by reference to the following specific embodiments and examples contained therein.

[0039] Before the present compounds, devices and / or methods are disclosed and described, it should be understood that, unless otherwise indicated, they are not limited to specific synthetic methods or specific reagents, as these may of course vary. It should also be understood that the terminology used in the present invention is used only for the purpose of describing certain embodiments, 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 following exemplary methods and materials are described.

[0040] The term "optionally" or "optionally" as used herein means that the subsequently described event or condition may or may not occur, and that the description includes situations in which the aforementioned event or condition occurs and situations in which it does not occur.

[0041] Disclosed herein are the components that can be used in the preparation of the compositions described in the present invention, and the compositions themselves to be used in the methods disclosed in the present invention. When these and other substances are disclosed in the present invention, and combinations, subsets, interactions, groups, etc. of these substances are disclosed, each individual and collective combination, permutation, and combination of these compounds, even if specific references thereto cannot be explicitly disclosed, should be understood to be specifically contemplated and described in the present invention. For example, when a particular compound is disclosed and discussed, and many modifications that can be made to many molecules containing the compound are discussed, each combination and permutation of the compound, and the possible modifications, are specifically contemplated, unless explicitly indicated to the contrary. Thus, if certain molecules A, B, C and certain molecules D, E, F are disclosed, as well as an example of combining molecule A-D, each is individually and collectively contemplated, even if not individually described, meaning that combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, C-F are considered to be disclosed. Similarly, any subset or combination thereof is also disclosed. Thus, for example, subgroups of A-E, B-F and C-E should be considered to be disclosed. This concept applies to all aspects of the present invention, including, but not limited to, the steps in the methods of preparing and using the compositions. Thus, if there are various additional steps that are possible, each of these additional steps should be understood to be possible by a specific embodiment or combination of embodiments of the method.

[0042] A linking atom as used in the present invention can link two groups, such as an N group and a C group. The linking atom can optionally (if valences permit) have other linked chemical moieties. For example, in one embodiment, an oxygen, once bonded to two atoms (e.g., N or C), will not bond to any other chemical moieties since the valences are satisfied. In contrast, when a carbon is a linking atom, two more chemical moieties can be bonded 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 groups.

[0043] As used herein, the term "cyclic structure" or similar terms refers to any cyclic chemical structure, including, but not limited to, aryl groups, heteroaryl groups, cycloalkyl groups, heterocyclyl groups, carbenes, and N-heterocyclic carbenes.

[0044] The term "substituted" as used herein is intended to include all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. For appropriate organic compounds, the permissible substituents can be one or more and can be the same or different. For purposes of this invention, a heteroatom (e.g., nitrogen) can have hydrogen substituents and / or any permissible substituent of organic compounds described herein that satisfies the valence of the heteroatom. This disclosure is not intended to be limited in any manner by the permissible substituents of organic compounds. Similarly, the terms "substituted" or "substituted with" include the implicit proviso that such substitution is compatible with the atom being substituted and the permissible valences 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 embodiments, unless specified to the contrary, individual substituents may be further optionally substituted (i.e., further substituted or unsubstituted).

[0045] In the definitions of various terms, "R 1 ", "R 2 ", "R 3 " and "R 4 " are used in this invention as generic symbols to represent various specific substituents. These symbols may be any substituent and are not limited to those disclosed in this invention. When they are defined as specific substituents in one context, they may be defined as several other substituents in other contexts.

[0046] The term "alkyl group" as used in the present invention refers to a branched or unbranched saturated hydrocarbon group having 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group may be substituted or unsubstituted. For example, the alkyl group may be substituted with one or more groups, including but not limited to any of the substituted alkyl groups, cycloalkyl groups, alkoxy groups, amino groups, halogens, hydroxy groups, nitro groups, silyl groups, sulfo-oxo, or mercapto groups described in the present invention. A "lower alkyl" group is an alkyl group having from 1 to 6 (eg, 1 to 4) carbon atoms.

[0047] Throughout the specification, the term "alkyl group" is generally used to refer to both unsubstituted and substituted alkyl groups. However, substituted alkyl groups may also be specifically referred to in the present invention by specifying the specific substituents on the alkyl group. For example, the term "halogenated alkyl group" or "halogenated alkyl group" specifically refers to an alkyl group substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine). The term "alkoxyalkyl group" specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below. The term "alkylamino group" specifically refers to an alkyl group substituted with one or more amino groups, as described below. When "alkyl group" is used in one context and a specific term such as "alkyl alcohol" is used in another context, it does not mean that the term "alkyl group" does not also refer to the specific term such as "alkyl alcohol".

[0048] This practice is also used for other groups described herein. That is, when a term such as "cycloalkyl group" refers to both unsubstituted and substituted cycloalkyl group portions, the substituted portions can be more specifically identified in the present invention, for example, a particular substituted cycloalkyl group can be referred to as an "alkylcycloalkyl group", etc. Similarly, a substituted alkoxy group can be specifically referred to as, for example, a "halogenated alkoxy group", a particular substituted alkenyl group can be, for example, an "alkenyl alcohol", etc. Similarly, the practice of using a general term such as "cycloalkyl group" and a specific term such as "alkylcycloalkyl group" is not intended to indicate that the general term does not also include the specific term.

[0049] The term "cycloalkyl group" as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms. Illustrative examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, and the like. The term "heterocycloalkyl group" is a type of cycloalkyl group as defined above and is included within the meaning of the term "cycloalkyl group" in which at least one of the ring carbon atoms is replaced with a heteroatom, such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkyl groups and heterocycloalkyl groups can be substituted or unsubstituted. Cycloalkyl groups and heterocycloalkyl groups can be substituted with one or more groups, including, but not limited to, alkyl groups, cycloalkyl groups, alkoxy groups, amino groups, halogens, hydroxy groups, nitro groups, silyl groups, sulfo-oxo, or mercapto groups as described herein.

[0050] The term "polyolefin group" as used herein means a group having two or more CH 2 The term "polyolefin group" is used to refer to a group that contains a -(CH 2 ) a-, where "a" is an integer from 2 to 500.

[0051] As used herein, the terms "alkoxy" and "alkoxy group" are used to refer to an alkyl or cycloalkyl group attached through an ether linking group. That is, an "alkoxy group" is an alkyl group such as -OR 1 can be defined as follows, of which R 1 is an alkyl or cycloalkyl group as defined above. The term "alkoxy group" also includes polymeric alkoxy groups as just described. That is, an alkoxy group is an alkyl group such as -OR 1 -OR 2 -OR 1 -(OR 2 ) a -OR 3 where "a" is an integer from 1 to 200, and R 1 , R 2 and R 3 are each independently an alkyl group, a cycloalkyl group, or a combination thereof.

[0052] The term "alkenyl group" as used herein means a hydrocarbon group having 2 to 24 carbon atoms and whose structural formula contains at least one carbon-carbon double bond. 1 R 2 )C=C(R 3 R 4 ), are intended to include the E and Z isomers. This can be assumed in the structural formulae of the present invention where an asymmetric alkene is present, which can also be clearly indicated by the bond symbol C=C. The alkenyl group can be substituted with one or more groups, including but not limited to alkyl groups, cycloalkyl groups, alkoxy groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, cycloalkynyl groups, aryl groups, heteroaryl groups, aldehyde groups, amino groups, carboxyl groups, ester groups, halogens, hydroxy groups, carbonyl groups, azido groups, nitro groups, silyl groups, sulfo-oxo or mercapto groups as described in the present invention.

[0053] The term "cycloalkenyl group" as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms and containing at least one carbon-carbon double bond, i.e., C=C. Illustrative examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, norbornenyl, and the like. The term "heterocycloalkenyl group" is a type of cycloalkenyl group as defined above and is included within the meaning of the term "cycloalkenyl group", where at least one of the ring carbon atoms is replaced 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, hydroxy, carbonyl, azide, nitro, silyl, sulfo-oxo, or mercapto groups described herein.

[0054] The term "alkynyl group" as used herein refers to a hydrocarbon group having 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon triple bond. The alkynyl group may be unsubstituted or substituted with one or more groups, including but not limited to alkyl groups, cycloalkyl groups, alkoxy groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, cycloalkynyl groups, aryl groups, heteroaryl groups, aldehyde groups, amino groups, carboxyl groups, ester groups, halogens, hydroxy groups, carbonyl groups, azido groups, nitro groups, silyl groups, sulfo-oxo groups, or mercapto groups as described herein.

[0055] The term "cycloalkynyl group" as used in the present invention is a non-aromatic carbon-based ring containing at least 7 carbon atoms and at least one carbon-carbon triple bond. Examples of cycloalkynyl groups include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, etc. The term "heterocycloalkynyl group" is a type of cycloalkenyl group as defined above and is included in the meaning of the term "cycloalkynyl group", where at least one of the ring carbon atoms is replaced with a heteroatom, such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkynyl and heterocycloalkynyl groups can be substituted or unsubstituted. The cycloalkynyl and heterocycloalkynyl 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, hydroxy, carbonyl, azide, nitro, silyl, sulfo-oxo, or mercapto groups as described herein.

[0056] The term "aryl group" as used in the present invention refers to a group that contains any carbon-based aromatic group, including, but not limited to, benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term "aryl group" also includes "heteroaryl group", which is defined as a group that contains an aromatic group, where the aromatic group has at least one heteroatom incorporated in the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term "non-heteroaryl group" (also included in the term "aryl group") is defined as a group that contains an aromatic group, where the aromatic group does not contain a heteroatom. 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 groups, cycloalkyl groups, alkoxy groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, cycloalkynyl groups, aryl groups, heteroaryl groups, aldehyde groups, amino groups, carboxyl groups, ester groups, halogens, hydroxy groups, carbonyl groups, azide groups, nitro groups, silyl groups, sulfo-oxo or mercapto groups according to the present invention. The term "biaryl" is a specific type of aryl group and is included within the definition of "aryl". Biaryl refers to two aryl groups bonded together through a fused ring structure, such as naphthalene, or two aryl groups bonded through one or more carbon-carbon bonds, such as biphenyl.

[0057] The term "aldehyde" as used herein is represented by the formula -C(O)H. Throughout the specification, "C(O)" is a shorthand notation for a carbonyl group (i.e., C=O).

[0058] As used herein, the term "amine" or "amino group" refers to a group of the formula -NR 1 R 2 where R 1 and R 2may be independently selected from hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, or a heteroaryl group.

[0059] The term "alkylamino group" as used herein is represented by the formula -NH(-alkyl group), where alkyl group is as described herein. Representative examples include, but are not limited to, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, (sec-butyl)amino group, (tert-butyl)amino group, pentylamino group, isopentylamino group, (tert-pentyl)amino group, hexylamino group, etc.

[0060] The term "dialkylamino group" as used herein means a group of the formula -N(alkyl group) 2 where the alkyl group is as described in the present invention. 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.

[0061] The term "carboxylic acid" as used herein is represented by the formula -C(O)OH.

[0062] As used herein, the term "ester" refers to an ester of the formula -OC(O)R 1 Or -C(O)OR 1 where R 1 may be an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group or a heteroaryl group according to the present invention. 1O(O)CR 2 -C(O)O) a -or-(R 1 O(O)CR 2 -OC(O) a - where R 1 and R 2 can independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein, and "a" is an integer from 1 to 500. The term "polyester" is used to describe a group resulting from the reaction between a compound having at least two carboxyl groups and a compound having at least two hydroxyl groups.

[0063] The term "ether" as used herein means a group of the formula R 1 OR 2 where R 1 and R 2 may independently be an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, or a heteroaryl group as described herein. 1 OR 2 O) a - where R 1 and R 2 can independently be an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, or a heteroaryl group as described herein, and "a" is an integer from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutylene oxide.

[0064] As used herein, the term "halogen" refers to the halogens fluorine, chlorine, bromine and iodine.

[0065] As used herein, the term "heterocyclyl" refers to monocyclic and polycyclic non-aromatic ring systems, and as used herein the term "heteroaryl" refers to monocyclic and polycyclic aromatic ring systems in which at least one of the ring members is not carbon. The term includes azetidine, dioxane, furan, imidazole, isothiazole, isoxazole, morpholine, oxazole, oxazole (including 1,2,3-oxadiazole, 1,2,5-oxadiazole and 1,3,4-oxadiazole), piperazine, piperidine, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, tetrahydrofuran, tetrahydropyran, tetrazine (including 1, 2,4,5-tetrazine group), tetrazole group (including 1,2,3,4-tetrazole group and 1,2,4,5-tetrazole group), thiadiazole group (including 1,2,3-thiadiazole group, 1,2,5-thiadiazole group and 1,3,4-thiadiazole group), thiazole group, thiophene group, triazine group (including 1,3,5-triazine group and 1,2,4-triazine group), triazole group (including 1,2,3-triazole group and 1,3,4-triazole group), and the like.

[0066] The term "hydroxy group" as used herein is represented by the formula --OH.

[0067] The term "ketone" as used herein means a compound of the formula R 1 C(O)R 2 where R 1 and R 2 can independently be an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, or a heteroaryl group as described in this invention.

[0068] The term "azido group" as used herein means a group of the formula -N 3 It is represented by:

[0069] As used herein, the term "nitro group" refers to a group of the formula -NO 2 It is represented by:

[0070] The term "nitrile" as used herein is represented by the formula --CN.

[0071] The term "silyl group" as used herein means a group of the formula -SiR 1 R 2 R 3 where R 1 , R 2 and R 3 may independently be hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein.

[0072] As used herein, the term "sulfo-oxo group" refers to a group of the formula -S(O)R 1 , -S(O) 2 R 1 , -OS(O) 2 R 1 Or -OS(O) 2 OR 1 where R 1 can be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group according to the present invention. Throughout the specification, "S(O)" is an abbreviation for S=O. The term "sulfonyl" as used in the present invention refers to a group of the formula -S(O) 2 R 1 where R 1 can be an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, or a heteroaryl group. 1 S(O) 2 R 2 where R 1 and R 2can be independently an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, or a heteroaryl group as described herein. 1 S(O)R 2 where R 1 and R 2 can independently be an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, or a heteroaryl group as described in this invention.

[0073] The term "mercapto group" as used herein is represented by the formula -SH.

[0074] The present invention uses "R 1 ", "R 2 ", "R 3 ", "R n " (n is an integer) can independently have one or more of the groups listed above. For example, R 1 When is a straight chain alkyl group, one hydrogen atom of the alkyl group can be optionally replaced with a hydroxy group, an alkoxy group, an alkyl group, a halogen, etc. Depending on the group selected, the first group can be incorporated into the second group, or alternatively, the first group can be pendant (i.e., attached) to the second group. For example, for the phrase "an alkyl group comprising an amino group," the amino group can be incorporated within the backbone of the alkyl group. Also, alternatively, the amino group can be attached to the backbone of the alkyl group. The nature of the group selected will determine whether the first group is embedded or attached to the second group.

[0075] The compounds described in the present invention may contain "optionally substituted" moieties. In general, the term "substituted" (whether preceded by the term "optionally") means that one or more hydrogens of the designated moiety are replaced with a suitable substituent. Unless otherwise stated, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any depicted structure may be substituted with more than one substituent selected from a specified group, the substituents at each position may be the same or different. Combinations of substituents envisioned by the present invention are preferably those that result in the formation of stable or chemically feasible compounds. In certain embodiments, it is also encompassed that individual substituents may be further optionally substituted (i.e., further substituted or unsubstituted) unless expressly stated to the contrary.

[0076] The structure of the compound is: [ka] which can be expressed by the following formula: [ka] is understood to be equivalent to

[0077] where n is typically an integer, i.e., R n is five independent substituents R a(1) , R a(2) , R a(3) , R a(4) , R a(5) "Independent substituents" refers to the fact that each R substituent may be independently defined. For example, in certain circumstances, R a(m) is a halogen, R in that situation a(n) is not necessarily a halogen.

[0078] In the chemical structures and moieties disclosed and described herein, R 1 , R 2 , R 3 , R 4 , R 5, R 6 is mentioned many times in, etc. Unless otherwise explained, R in the specification 1 , R 2 , R 3 , R 4 , R 5 , R 6 etc. All explanations of, such as, apply to each of all the structures or parts that cite 1 , R 2 , R 3 , R 4 , R 5 , R 6 etc. respectively.

[0079] Due to various factors, optoelectronic devices using organic materials are becoming increasingly constrained. Since many of the materials used in the manufacture of such devices are relatively inexpensive, organic optoelectronic devices have the potential to be superior in terms of cost compared to inorganic devices. In addition, due to inherent properties such as flexibility, organic materials are very suitable for special applications such as manufacturing on flexible substrates. Examples of organic optoelectronic elements include organic EL elements (OLEDs), organic phototransistors, organic solar cells, and organic photodetectors. Regarding OLEDs, organic materials are considered to have a significant advantage in terms of performance compared to conventional materials. For example, the emission wavelength of the organic light-emitting layer can generally be adjusted with a suitable dopant.

[0080] Fluorescence refers to the instantaneous emission of light when an exciton decays from a singlet excited state to the ground state. Phosphorescence refers to the instantaneous emission of light when an exciton decays from a triplet excited state to the ground state. Phosphorescent metal complexes (e.g. platinum complexes) have already shown the potential to simultaneously utilize singlet and triplet excitons, achieving 100% internal quantum efficiency, due to the strong spin-orbit interaction between the singlet and triplet excited states of heavy metal atoms, which effectively enhances the intersystem crossing (ISC). Therefore, phosphorescent metal complexes are a good choice as dopants in the emissive layer of organic light-emitting diodes (OLEDs), which have attracted great attention in academic and industrial fields. Many achievements have already been achieved in the past decade, for example in the adoption of OLEDs in high-end displays in smartphones, televisions, and digital cameras, and the commercialization of the technology is bringing benefits.

[0081] However, the most difficult area in this technology is blue light-emitting diodes, and the stability of blue elements is a major issue. It has also been demonstrated that the selection of host materials is extremely important for the stability of blue elements. However, the triplet excited state (T1) of blue light-emitting materials has a very high minimum energy, which means that the minimum energy of the triplet excited state (T1) of the host material for blue elements should be even higher, which increases the difficulty of developing host materials for blue elements.

[0082] The metal complexes of the present invention can be customized or tailored for specific applications where it is desired to have specific emission or absorption properties. The optical properties of the metal complexes disclosed in the present invention can be tuned by changing the ligand structure surrounding the metal center or by changing the structure of the fluorescent emitter on the ligand. For example, in general, metal complexes of ligands with electron-donating or electron-withdrawing substituents can exhibit different optical properties in the emission and absorption spectra. The color of the metal complex can be tuned by modifying the fluorescent emitter or the conjugated group on the ligand.

[0083] The emission of the complexes of the present invention can be tuned, for example, from ultraviolet to near infrared, by changing the structure of the ligand or the fluorescent emitter. A fluorescent emitter is a group of atoms in an organic molecule that can absorb energy to generate a singlet excited state, and the singlet exciton decays quickly, resulting in instantaneous emission. In one embodiment, the complexes of the present invention can provide emission in most of the visible spectrum. In a specific example, the complexes of the present invention can emit light within the wavelength range of visible light or near infrared light. In another embodiment, the complexes of the present invention have improved stability and efficiency compared to conventional luminescent complexes. The complexes of the present invention can also be used as luminescent labels for biological applications, anticancer drugs, emitters in organic light-emitting diodes (OLEDs), or combinations thereof. In another embodiment, the complexes of the present invention can be used in light-emitting devices, for example, compact fluorescent lamps (CFLs), light-emitting diodes (LEDs), incandescent lamps, and combinations thereof.

[0084] The present specification discloses a platinum-containing compound or composite complex. The terms compound or complex are used interchangeably in the present invention. Also, the compound disclosed herein has a neutral charge.

[0085] The compounds disclosed herein can exhibit desired properties and have tunable emission and / or absorption spectra by selecting appropriate ligands. In another aspect, the present invention can exclude any one or more compounds, structures or portions thereof specifically described herein.

[0086] The compounds disclosed herein find application in a variety of optical and electro-optical devices, including, but not limited to, light absorbing devices such as solar devices and photosensitive devices, organic light emitting diodes (OLEDs), light emitting devices, or devices capable of absorbing and emitting light, and markers used in biological applications.

[0087] As mentioned above, the disclosed compounds are platinum complexes. At the same time, the disclosed compounds can be used as host materials for OLED applications, such as full-color displays.

[0088] The compounds disclosed herein can be used in a variety of applications, including as light-emitting materials in organic light-emitting diodes (OLEDs), light-emitting devices and displays, and other light-emitting elements.

[0089] Moreover, compared with conventional materials, the compounds of the present invention can be used in light-emitting devices (eg, OLEDs) to improve the luminous efficiency and operating time of the device.

[0090] The compounds of the present invention can be prepared in a variety of ways, including but not limited to those described in the examples provided herein.

[0091] The compound disclosed herein may be a delayed fluorescent and / or phosphorescent emitter. In one embodiment, the compound disclosed herein may be a delayed fluorescent emitter. In one embodiment, the compound disclosed herein may be a phosphorescent emitter. In another embodiment, the compound disclosed herein may be a delayed fluorescent emitter and a phosphorescent emitter.

[0092] The compounds disclosed in embodiments of the present invention find application in a variety of optical and electro-optical devices, including, but not limited to, light absorbing devices such as solar devices and photosensitive devices, organic light emitting diodes (OLEDs), light emitting devices, or devices that have both light absorbing and light emitting capabilities, as well as markers used in biological applications.

[0093] The compounds disclosed in the embodiments of the present invention can be used in light-emitting elements such as OLEDs. The element includes at least one cathode, at least one anode, and at least one light-emitting layer. At least one of the light-emitting layers contains the above-mentioned phenylcarbazole-based tetradentate cyclometalated platinum complex. Specifically, the light-emitting element may include an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode that are sequentially formed by deposition. Among them, the hole transport layer, the light-emitting layer, and the electron transport layer are all organic layers, and the anode and the cathode are electrically connected.

[0094] Examples of Synthesis

[0095] The following examples regarding the synthesis, components, devices, and methods of the compounds are for providing general methods for the relevant industrial field and are not for limiting the protection scope of the patent. Regarding the data (quantity, temperature, etc.) presented in this patent, efforts have been made to ensure accuracy, but there may still be some errors. Unless otherwise specified, all weighings are performed separately, the temperature is in °C or at room temperature, and the pressure is approximately atmospheric pressure.

[0096] The following examples provide methods for preparing new compounds, but the preparation of these compounds is not limited to these methods. In the technical field of this patent, the compounds protected in this patent are easy to modify and prepare. Therefore, for their preparation, the methods listed below can be adopted, or other methods can also be adopted. The following examples are only examples and are not for limiting the protection scope of the patent. In order to prepare the above-mentioned compounds by selecting different conditions for different reactants, the temperature, catalyst, concentration, reactants, and reaction steps can all be changed.

[0097] 1 H NMR (500 MHz), 13 The C NMR (126 MHz) spectra were measured on a Bruker AVANCE III (500 M) nuclear magnetic resonance spectrometer. Unless otherwise specified, all nuclear magnetic resonances were performed in DMSO-d 6 or CDCl containing 0.1% of TMS 3was used as the solvent. Here, 1 in the 1H NMR spectrum, when CDCl 3 was used as the solvent, TMS (δ = 0.00 ppm) was used as the internal standard, and when DMSO-d 6 was used as the solvent, either TMS (δ = 0.00 ppm), the residual DMSO peak (δ = 2.50 ppm), or the residual H 2 O peak (δ = 3.33 ppm) was used as the internal standard. 13 In the 13C NMR (126 MHz) spectrum, CDCl 3 (δ = 77.00 ppm) or DMSO-d 6 (δ = 39.52 ppm) was used as the internal standard. HPLC-MS was measured on an Agilent 6210 TOF LC / MS mass spectrometer. The HRMS spectrum was measured on an Agilent 6210 TOF LC / MS liquid chromatograph-time-of-flight mass spectrometer. 1 In the data of the 1H NMR spectrogram, s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad.

[0098] Synthesis Scheme

[0099] The general synthesis scheme is as follows.

[0100]

Chemical Structure

[0101] (Example 1) The platinum complex Pt1 can be synthesized according to the following scheme.

[0102]

Chemical Structure

[0103] Synthesis of intermediate 8-methoxyquinoline: 8-hydroxyquinoline (5.00g, 34.5mmol, 1.00Eq) and N,N-dimethylformamide (40mL) were added to a 100mL three-neck flask equipped with a magnetic rotor, then placed in a low-temperature bath and stirred. After the temperature had dropped, sodium hydride (1.38g, 34.5mmol, 1.00Eq) with a mass fraction of 60% was gradually added, and the mixture was left at room temperature, after which iodomethane (5.14g, 36.3mmol, 1.05Eq) was added and reacted for 8 hours. The reaction mixture was quenched by adding ethanol, and the solvent was removed by distillation under reduced pressure, and then extracted three times with ethyl acetate. The organic phases were combined and dried by adding anhydrous sodium sulfate, and the obtained crude product was separated and purified by silica gel column chromatography, the eluent (petroleum ether / acetone) was 2:1, and the solvent was removed by distillation under reduced pressure, obtaining a dark red solid (4.76g, 87% yield). 1 H NMR (400 MHz, CDCl 3 ): δ4.10(s,3H),7.06(d,J=8.0Hz,1H),7.38-7.49(m,3H),8.13(d,J=8.0Hz,1H),8.94(dd,J=3.6Hz,0.8Hz,1H).

[0104] Synthesis of intermediate 1-NO: 8-Methoxyquinoline (5.4g, 34.2mmol, 1.00Eq) and dichloromethane (170mL) were added to a 500mL three-necked flask equipped with a magnetic rotor, then the three-necked flask was fixed in a low-temperature reaction bath, and after the temperature had dropped, metachloroperbenzoic acid (8.84g, 51.3mmol, 1.50Eq) was gradually added, the three-necked flask was removed, and the reaction was carried out at room temperature for 24 hours. The reaction mixture was quenched by adding sodium thiosulfate, diluted with water, and then extracted with dichloromethane 4-5 times, and the solvent was removed by vacuum distillation to obtain the crude product as a dark red solid (4.15g, 69% yield). It was used as it was in the next step.

[0105] Synthesis of intermediate 2-bromo-8-methoxyquinoline: In a 1000mL three-necked flask equipped with a magnetic rotor, intermediate 1-NO (6.90g, 39.4mmol, 1.00Eq), n-butylammonium bromide (19.05g, 59mmol, 1.50Eq), and molecular sieves were added in that order, and 700mL of dichloromethane was added. After stirring at room temperature for 10 minutes, p-toluenesulfonic anhydride (19.28g, 59mmol, 1.50Eq) was added and reacted at room temperature for 24 hours. The reaction mixture was filtered, the filter cake was washed with dichloromethane, and the obtained crude product was separated and purified by silica gel column chromatography, the eluent (petroleum ether / ethyl acetate) was 10:1, and the solvent was removed by vacuum distillation to obtain a white solid (4.3g, yield 46%). 1 H NMR (400 MHz, CDCl 3 ): δ4.06(s,3H),7.08(d,J=8.0Hz,1H),7.37(d,J=8.0Hz,1H),7.47-7.51(m,1H),7.55(d,J=8.8Hz,1H),7.96(d,J=8.8Hz,1H).

[0106] Synthesis of intermediate L1-Me: In a 50 mL three-neck flask equipped with a magnetic stirrer, add 2-bromo-8-methoxyquinoline (277 mg, 1.16 mmol, 1.10 Eq), M-1 (420 mg, 1.06 mmol, 1.00 Eq), Pd(PPh 3 ) 4 (35mg, 0.03mmol, 0.03Eq), K 2 CO 3 (365 mg, 2.65 mmol, 2.50 Eq) were added in that order, and the mixture was purged with nitrogen three times, followed by dioxane / H 2 O=6:1 mL was poured in, the temperature was raised to 85℃, and the reaction was carried out for 24 hours. The reaction mixture was quenched by adding water, diluted with ethyl acetate, extracted three times with ethyl acetate, and then dried by adding anhydrous sodium sulfate. The obtained crude product was separated and purified by silica gel column chromatography, the eluent (petroleum ether / ethyl acetate) was 8:1, and the solvent was removed by distillation under reduced pressure to obtain a white foamy solid (348 mg, yield 75%). 1 H NMR (400 MHz, CDCl3 ):δ1.69(s,6H),4.06(s,3H),6.87(dd,J=8.0,1.2Hz,1H),7.02-7.12(m,3H),7.28(d,J=0.8Hz,1H),7.36-7.42(m,3H),7.48(dd,J=7 .6,1.2Hz,1H),7.57-7.59(m,2H),7.71(d,J=8.4Hz,1H),7.82-7.88(m,2H),8.10(d,J=8.4Hz,1H),8.94(ddd,J=4.8,2.0,0.8Hz,1H).

[0107] Synthesis of intermediate L1: L1-Me (280 mg, 0.63 mmol, 1.00 Eq) and pyridine hydrochloride (912 mg, 6.3 mmol, 10.00 Eq) were added in this order to a 50 mL three-neck flask equipped with a magnetic rotor, and after three nitrogen purges, 3 mL of 1,3-dimethyl-2-imidazolidinone was poured in and the temperature was raised to 180 °C for 24 hours. The reaction mixture was quenched by adding 100 mL of water, extracted three times with ethyl acetate, and then the organic phases were combined, dried with anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The obtained crude product was separated and purified by silica gel column chromatography, and the eluent (petroleum ether / ethyl acetate) was 15:1. The solvent was removed by distillation under reduced pressure to obtain a white foamy solid (175 mg, yield 65%). 1 H NMR (400MHz, DMSO-d 6 ):δ1.63(s,6H),6.75 (dd,J=8.0Hz,1.2Hz,1H),7.03-7.14(m,3H),7.36-7.47(m,4H),7.54(dd,J=7.6Hz,1.6Hz,1H),7.61 (d,J=2.0Hz,1H),7.66(d,J=8.4Hz,1H),7.84(d,J=8.8Hz,1H),8.01(td,J=7.6Hz,2.0Hz,1H),8 .08(dd,J=8.0Hz,1.6Hz,1H),8.32(d,J=8.4Hz,1H),8.94(dt,J=4.8Hz,1.6Hz,1H),9.40(s,1H).

[0108] Synthesis of Pt1: L1 (140mg, 0.33mmol, 1.00Eq) and potassium tetrachloroplatinate (143mg, 0.35mmol, 1.05Eq) were added in this order to a 50mL three-neck flask equipped with a magnetic rotor, and nitrogen purging was performed three times, followed by injection of acetic acid. Nitrogen gas was bubbled for 30 minutes, and the mixture was stirred at room temperature for 8 hours, then the temperature was raised to 120°C and reacted for 24 hours. After the reaction mixture was distilled under reduced pressure to remove 30mL of acetic acid, the reaction mixture was separated and purified by silica gel column chromatography, and the eluent (dichloromethane / ethyl acetate) was 15:1. The solvent was removed by distillation under reduced pressure, and the product was obtained as a dark red solid (170mg, yield 84%). 1 H NMR (400MHz, DMSO-d 6 ):δ1.34(s,3H),1.84(s,3H),5.76(s,1H),6.52(d,J=8.0Hz,1H),6.74(d,J=8.0Hz,1H ),7.07(d,J=8.0Hz,1H),7.21-7.25(m,4H),7.38(d,J=8.0Hz,1H),7.53-7.56(m,2H), 7.78(d,J=8.8Hz,1H),8.00-8.05(m,1H),8.17(d,J=8.8Hz,1H),8.88(dd,J=6.0Hz,2.0Hz,1H).

[0109] Example 2 The platinum complex Pt2 can be synthesized according to the following scheme.

[0110] [ka]

[0111] Synthesis of L2-Me: In a 50 mL three-neck flask equipped with a magnetic stirrer, add 2-bromo-8-methoxyquinoline (234 mg, 0.99 mmol, 1.05 Eq), B (400 mg, 0.94 mmol, 1.00 Eq), Pd(PPh 3 ) 4 (32.5mg, 0.03mmol, 0.03Eq), K 2 CO 3(324 mg, 2.34 mmol, 2.50 Eq) were added in that order, and the mixture was purged with nitrogen three times, followed by dioxane / H 2 O=6:1 mL was poured in, the temperature was raised to 85℃, and the reaction was carried out for 24 hours. The reaction mixture was quenched by adding water, diluted with ethyl acetate, extracted three times with ethyl acetate, and then dried by adding anhydrous sodium sulfate. The obtained crude product was separated and purified by silica gel column chromatography, the eluent (petroleum ether / ethyl acetate) was 6:1, and the solvent was removed by distillation under reduced pressure to obtain a white foamy solid (333 mg, yield 78%). 1 H NMR (500 MHz, CDCl 3 ):δ1.70(s,6H),2.41(s,3H),4.05(s,3H),6.69(dd,J=8.0Hz,1.5Hz,1H),7.00-7.08(m, 3H),7.14-7.15(m,1H),7.22(t,J=0.5Hz,1H),7.34-7.43(m,3H),7.47(dd,J=7.5Hz,1.5 Hz,1H),7.58(d,J=8.0Hz,1H),7.67(d,J=8.5Hz,1H),7.82(dd,J=8.0Hz,1.5Hz,1H),8.09(d,J=8.5Hz,1H),8.61(d,J=5.0Hz,1H).

[0112] Synthesis of intermediate L2: L2-Me (320 mg, 0.7 mmol, 1.00 Eq) and pyridine hydrochloride (808 mg, 7 mmol, 10.00 Eq) were added in this order to a 50 mL three-neck flask equipped with a magnetic rotor, and after three nitrogen purges, 3 mL of 1,3-dimethyl-2-imidazolidinone was poured in and the temperature was raised to 180 °C for 24 hours. The reaction mixture was quenched by adding 100 mL of water, extracted three times with ethyl acetate, and then the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The obtained crude product was separated and purified by silica gel column chromatography, and the eluent (petroleum ether / ethyl acetate) was 15:1. The solvent was removed by distillation under reduced pressure to obtain a white foamy solid (224 mg, 72% yield). 1 H NMR (500 MHz, CDCl 3):δ1.73(s,6H),2.44(s,3H),6.63(dd,J=9.0Hz,1.5Hz1H),7.00-7.08(m,2H),7.14(dd,J=7.5Hz,1.0Hz,1H),7.21-7.22(m,1H),7.24(d,J=0.5Hz) ,1H),7.29(dd,J=8.0Hz,1.0Hz,1H),7.39(t,J=8.0Hz,1H),7.47-7.49(m,2H),7.69(d,J=8.0Hz,1H),7.71(dd,J=8.5Hz,2.0Hz,1H),7.76(d,J=9.0 Hz,1H),8.61(d,J=5.0Hz,1H),8.66(d,J=5.0Hz,1H).

[0113] Synthesis of Pt2: L2 (220 mg, 0.49 mmol, 1.00 Eq) and potassium tetrachloroplatinate (216 mg, 0.52 mmol, 1.05 Eq) were added in this order to a 50 mL three-neck flask equipped with a magnetic rotor, and nitrogen purging was performed three times, followed by injection of 30 mL of acetic acid. Nitrogen gas was bubbled for 30 minutes, and the mixture was stirred at room temperature for 8 hours, then heated to 120°C and reacted for 24 hours. The reaction mixture was distilled under reduced pressure to remove acetic acid, and then separated and purified by silica gel column chromatography. The eluent (dichloromethane / ethyl acetate) was 20:1, and the solvent was distilled under reduced pressure to remove the product, resulting in a pale red solid (170 mg, yield 94%). 1 H NMR (500MHz, DMSO-d 6 ):δ1.35(s,3H),1.84(s,3H),2.24(s,3H),6.53(dd,J=7.5Hz,0.5Hz,1H),6.75(d,J=8.0Hz,1H),7.07(d,J=7.5Hz,1H),7.10(dd,J=6.5Hz,1 .5Hz,1H),7.20-7.25(m,4H),7.37(t,J=4.5Hz,2H),7.52-7.54(m,1H),7.76(d,J=8.5Hz,1H),8.17(d,J=9.0Hz,1H),8.73(d,J=6.5Hz,1H).

[0114] Example 3 The platinum complex Pt3 can be synthesized according to the following scheme.

[0115] [Chemistry]

[0116] Synthesis of 5-Bromo-8-methoxyquinoline: 8-Methoxyquinoline (4.76 g, 29.9 mmol, 1.00 Eq) was added to a 500 mL three-necked flask equipped with a magnetic stirrer. After adding 230 mL of acetonitrile, N-bromosuccinimide (5.32 g, 31.3 mmol, 1.05 Eq) was gradually added, and the mixture was reacted for 8 hours. An aqueous sodium sulfite solution was added to the reaction mixture to quench the reaction, and dichloromethane was added for dilution. The mixture was extracted three times with dichloromethane, and then the organic phases were combined and dried over anhydrous sodium sulfate. The crude product was separated and purified by silica gel column chromatography, and the eluent (dichloromethane / ethyl acetate) was 10:1. The solvent was removed by distillation under reduced pressure to obtain a pale yellow solid (5.8 g, yield 82%). It was used directly in the next reaction.

[0117] Synthesis of Intermediate 3-A: In a reaction tube equipped with a magnetic stirrer, 5-Bromo-8-methoxyquinoline (500 mg, 2.1 mmol, 1.00 Eq), 4-tert-Butylphenylboronic acid (374 mg, 2.1 mmol, 1.00 Eq), Pd(PPh 3 ) 4 (73 mg, 0.06 mmol, 0.03 Eq), and K 2 CO 3 (726 mg, 5.25 mmol, 2.5 Eq) were added in sequence. After purging with nitrogen three times, 8 mL of dioxane / H 2 O = 8:2 was injected, and the temperature was raised to 85 °C and reacted for 24 hours. Ethyl acetate was added to the reaction mixture for dilution, and the mixture was extracted three times with ethyl acetate and then dried over anhydrous sodium sulfate. The crude product was separated and purified by silica gel column chromatography, and the eluent (petroleum ether / ethyl acetate) was 3:2. The solvent was removed by distillation under reduced pressure to obtain a white solid (580 mg, yield 94%). 1 1H NMR (400 MHz, CDCl 3):δ1.40(s,9H),4.14(s,3H),7.11(d,J=8.0Hz,1H),7.37-7.40(m,3H),7.44(d,J=8.0H z,1H),7.49-7.52(m,2H),8.28(dd,J=8.4Hz,1.6Hz,1H),8.94(dd,J=8.4Hz,2.0Hz,1H).

[0118] Synthesis of intermediate 3-NO: 3-A (5.00g, 17.2mmol, 1.00Eq) and dichloromethane (100mL) were added to a 500mL three-necked flask equipped with a magnetic rotor, and the three-necked flask was fixed in a low-temperature reaction bath. After the temperature had dropped, metachloroperbenzoic acid (5.9g, 34.4mmol, 2.00Eq) was gradually added, and the three-necked flask was removed and reacted at room temperature for 24 hours. The reaction mixture was quenched by adding sodium thiosulfate, diluted with water, and then extracted with dichloromethane 4-5 times, and the solvent was removed by vacuum distillation. The crude product was separated and purified by silica gel column chromatography to obtain a dark red solid (2.1g, 40% yield). It was used as it was in the next step.

[0119] Synthesis of intermediate 3-Br: In a 500mL three-necked flask equipped with a magnetic rotor, intermediate 3-NO (2.1g, 7.2mmol, 1.00Eq), n-butylammonium bromide (3.48g, 10.81mmol, 1.50Eq), and molecular sieves were added in that order, followed by dichloromethane (180mL), which was stirred at room temperature for 10 minutes, followed by p-toluenesulfonic anhydride (3.53g, 10.81mmol, 1.50Eq), which was stirred at room temperature overnight, and reacted for 24 hours. The reaction mixture was filtered, the filter cake was washed with dichloromethane, and the solvent was removed by vacuum distillation. The obtained crude product was separated and purified by silica gel column chromatography, the eluent (petroleum ether / ethyl acetate) was 20:1, and the solvent was removed by vacuum distillation to obtain a pale yellow solid (800mg, yield 30%). 1 H NMR (400 MHz, CDCl 3): δ 1.40 (s, 9H), 4.10 (s, 3H), 7.13 (d, J = 8.0 Hz, 1H), 7.33 - 7.35 (m, 2H), 7.44 - 7.52 (m, 4H), 8.10 (d, J = 8.8 Hz, 1H).

[0120] Synthesis of Intermediate L3-Me: In a reaction tube equipped with a magnetic rotor, 3-Br (150 mg, 0.4 mmol, 1.00 Eq), M-1 (175 mg, 0.43 mmol, 1.05 Eq), Pd(PPh 3 ) 4 (15 mg, 0.01 mmol, 0.03 Eq), K 2 CO 3 (140 mg, 1.01 mmol, 2.50 Eq) were added in sequence. After purging with nitrogen three times, 6:1 mL of dioxane / H 2 O was injected, the temperature was raised to 85 °C, and the reaction was carried out for 24 hours. Water was added to the reaction mixture to quench it, ethyl acetate was added to dilute it, and it was extracted three times with ethyl acetate and then dried over anhydrous sodium sulfate. The obtained crude product was separated and purified by silica gel column chromatography, and the eluent (petroleum ether / ethyl acetate) was 5:1. The solvent was removed by distillation under reduced pressure to obtain a white foamy solid (170 mg, yield 81%). 1 H NMR (500 MHz, CDCl 3 ): δ 1.40 (s, 9H), 1.69 (s, 6H), 4.09 (s, 3H), 6.83 (dd, J = 8.0 Hz, 1.5 Hz, 1H), 7.02 - 7.10 (m, 3H), 7.25 - 7.28 (m, 1H), 7.36 - 7.40 (m, 4H), 7.47 - 7.51 (m, 3H), 7.54 (d, J = 2.0 Hz, 1H), 7.59 (t, J = 8.0 Hz, 1H), 7.63 (d, J = 9.0 Hz, 1H), 7.84 (ddd, J = 8.0 Hz, 7.5 Hz, 2.0 Hz, 1H), 7.88 (dd, J = 8.0 Hz, 1.5 Hz, 1H), 8.23 (d, J = 9.0 Hz, 1H), 8.70 (ddd, J = 5.0 Hz, 2.0 Hz, 1.0 Hz, 1H).

[0121] Synthesis of intermediate L3: L3-Me (170 mg, 0.30 mmol, 1.00 Eq) and pyridine hydrochloride (341 mg, 3 mmol, 10.00 Eq) were added in this order to a reaction tube equipped with a magnetic rotor, and after three nitrogen purges, 3 mL of 1,3-dimethyl-2-imidazolidinone was poured in, and the temperature was raised to 180 ° C. and reacted for 24 hours. The reaction mixture was quenched by adding 100 mL of water, extracted three times with ethyl acetate, and then the organic phases were combined, dried with anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The obtained crude product was separated and purified by silica gel column chromatography, and the eluent (petroleum ether / ethyl acetate) was 30:1. The solvent was removed by distillation under reduced pressure to obtain a pale yellow foamy solid (80 mg, yield 47%). 1 H NMR (500 MHz, CDCl 3 ):δ1.40(s,9H),1.72(s,6H),6.75(dd,J=8.0Hz,1.5Hz,1H),7.04(td,J=7.5Hz,1.5Hz,1H),7.09(td,J=7.5Hz,2.0Hz,1 H),7.34(ddd,J=7.5Hz,5.0Hz,1.0Hz,1H),7.36-7.40(m,3H),7.41(dt,J=9.0Hz,1.0Hz,1H),7.49-7.51(m,3H),7.60(d, J=4.5Hz,1H),7.61(d,J=9.0Hz,1H),7.71(d,J=9.0Hz,1H),7.76(dd,J=8.5Hz,2.0Hz,1H),7.89 (ddd,J=7.5Hz,5.5Hz,2.0Hz,1H),8.30(d,J=9.0Hz,1H),8.77(ddd,J=7.0Hz,2.0Hz,0.5Hz,1H).

[0122] Synthesis of Pt3: L3 (80mg, 0.14mmol, 1.00Eq) and potassium tetrachloroplatinate (61mg, 0.14mmol, 1.05Eq) were added in this order to a 50mL three-neck flask equipped with a magnetic rotor, and nitrogen purging was performed three times, followed by injection of 20mL of acetic acid. Nitrogen gas was bubbled for 30 minutes and the mixture was stirred at room temperature for 8 hours, then the temperature was raised to 120°C and reacted for 24 hours. The reaction mixture was distilled under reduced pressure to remove acetic acid, and then the reaction mixture was separated and purified by silica gel column chromatography, with an eluent (dichloromethane / ethyl acetate) of 30:1, and the solvent was removed by distillation under reduced pressure to obtain a dark red solid (95mg, yield 90%). 1 H NMR (500MHz, DMSO-d 6 ):δ1.34(s,9H),1.34(s,3H),1.84(s,3H),6.01(d,J=8.0Hz,1H),7.05-7.13(m,2H),7.21-7.26(m,4H),7.35(d,J=8.0Hz,1H),7.38-7.39(m ,2H),7.50-7.52(m,2H),7.53-7.57(m,2H),7.75(d,J=9.0Hz,1H),8.02-8.05(m,1H),8.13(d,J=9.0Hz,1H),8.90(dd,J=6.0Hz,1.5Hz,1H).

[0123] Example 4 The platinum complex Pt42 can be synthesized according to the following scheme.

[0124] [ka]

[0125] Synthesis of intermediate L42-Me: In a reaction tube equipped with a magnetic stirrer, add 3-Br (130 mg, 0.35 mmol, 1.00 Eq), M-2 (149 mg, 0.35 mmol, 1.00 Eq), Pd(PPh 3 ) 4 (12.2mg, 0.01mmol, 0.03Eq), K 2 CO 3(96.7 mg, 0.7 mmol, 2.0 Eq) were added in that order, and the mixture was purged with nitrogen three times, followed by dioxane / H 2 O=5:1 mL was poured in, the temperature was raised to 85℃, and the reaction was carried out for 24 hours. The reaction mixture was quenched by adding water, diluted with ethyl acetate, extracted three times with ethyl acetate, and then dried by adding anhydrous sodium sulfate. The obtained crude product was separated and purified by silica gel column chromatography, the eluent (petroleum ether / ethyl acetate) was 10:1, and the solvent was removed by distillation under reduced pressure to obtain a white foamy solid (190 mg, yield 91%). 1 H NMR (500 MHz, CDCl 3 ):δ1.40(s,9H),1.70(s,6H),2.40(s,3H),4.09(s,3H),6.67-6.72(m,1H),7.02(t,J=6.0Hz,1H ),7.05-7.09(m,2H),7.13(d,J=5.0Hz,1H),7.22(s,1H),7.36-7.40(m,4H),7.47-7.51(m,3H), 7.59(d,J=8.0Hz,1H),7.62(d,J=9.0Hz,1H),7.87(dd,J=8.0Hz,1.0Hz,1H),8.24(d,J=9.0Hz,1H),8.61(d,J=5.0Hz,1H).

[0126] Synthesis of intermediate L42: L3-Me (180 mg, 0.30 mmol, 1.00 Eq) and pyridine hydrochloride (352 mg, 3 mmol, 10.00 Eq) were added in this order to a reaction tube equipped with a magnetic rotor, and after three nitrogen purges, 3 mL of 1,3-dimethyl-2-imidazolidinone was poured in, and the temperature was raised to 180 ° C. and reacted for 24 hours. The reaction mixture was quenched by adding saturated sodium bicarbonate solution, extracted three times with ethyl acetate, and then the organic phases were combined, dried with anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The obtained crude product was separated and purified by silica gel column chromatography, and the eluent (petroleum ether / ethyl acetate) was 30:1. The solvent was removed by distillation under reduced pressure to obtain a pale yellow solid (153 mg, yield 87%). 1 H NMR (500 MHz, CDCl 3):δ1.40(s,9H),1.73(s,6H),2.44(s,3H),6.66(d,J=7.5Hz,1H),7.02-7.10(m,2H),7.21-7.22(m,2H),7.24-7.27(m,2H),7 .37-7.39(m,3H),7.48-7.51(m,4H),7.61(d,J=8.0Hz,1H),7.71-7.75(m,2H),8.33(d,J=8.5Hz,1H),8.66(d,J=5.0Hz,1H).

[0127] Synthesis of Pt42: L3 (130mg, 0.23mmol, 1.00Eq) and potassium tetrachloroplatinate (98.4mg, 0.23mmol, 1.05Eq) were added in this order to a 50mL three-neck flask equipped with a magnetic rotor, and nitrogen purging was performed three times, and 14mL of acetic acid was injected. Nitrogen gas was bubbled for 30 minutes and stirred at room temperature for 8 hours, then the temperature was raised to 120°C and reacted for 24 hours. The reaction mixture was distilled under reduced pressure to remove acetic acid, and then the reaction mixture was separated and purified by silica gel column chromatography, with an eluent (dichloromethane / ethyl acetate) of 30:1, and the solvent was removed by distillation under reduced pressure to obtain a dark red solid (140mg, yield 81%). 1 H NMR (500MHz, DMSO-d 6 ):δ1.34(s,9H),1.35(s,3H),1.83(s,3H),2.24(s,3H),6.60(d,J=8.0Hz,1 H),7.07(d,J=8.0Hz,1H),7.11(dd,J=1.5,6.0Hz,1H),7.20-7.22(m,3H),7 .23(d,J=8.0Hz,1H),7.34(d,J=8.0Hz,1H),7.37-7.39(m,3H),7.50-7.54( m,3H),7.74(d,J=9.0Hz,1H),8.12(d,J=9.0Hz,1H),8.75(d,J=6.0Hz,1H).

[0128] Explanation of optical properties tests and theoretical calculations

[0129] Steady-state emission experiments and lifetime measurements were performed using a Horiba Jobin Yvon FluoroLog-3 spectrometer. Theoretical calculations for the Pt(II) complexes were performed using the Titan software package. Density functional theory (DFT) was utilized to calculate the ground state (S 0 The molecular geometry was optimized in the 3D structure of the 1D-type ...

[0130] [ka]

[0131] From Figures 1 to 3, it can be seen that the platinum complexes Pt1, Pt2, Pt3 and Pt42 can emit strong light in dichloromethane solution, with the maximum emission wavelengths of 549 nm, 547 nm, 534 nm and 608 nm, respectively, and the quantum efficiency of the solutions all exceeding 40%. 2 The quantum efficiency of the solution was only about 1.5% (I. Taydakov, K. Lyssenko, R. Saifutyarov, A. Akkuzina, R. Avetisov, A. Mozhevitina, I. Avetissov. Dyes and Pigments, 2016, 135, 80-85). From these results, it can be seen that the quantum efficiency of the tetradentate-based platinum complex of this application can be greatly improved compared to the bidentate platinum complex.

[0132] Table 1 shows the frontier orbital distribution energy levels for some platinum complexes obtained in the experimental part of the theoretical calculations.

[0133] [Table 1]

[0134] [ka] JPEG0007681866000032.jpg66155

[0135] figure 5 As can be seen from the figure, in comparison with Pt1, Pt2 has a methyl group introduced into the pyridine, and the highest occupied molecular orbital ( HOMO ), lowest empty orbit ( LUMO ) is small, the change in ΔE is small, and the maximum emission wavelength is close, but the molecular stability can be increased. Compared with Pt1, Pt3 has a 4-tert-butylphenyl group introduced into the quinoline part, which obviously delocalizes the HOMO distribution, but the effect on the LUMO distribution is not so large, and ΔE is reduced, but the spectrum is blue-shifted. This is thought to be due to the molecular emission spectrum being blue-shifted due to the triplet energy level being higher. At the same time, the introduction of the 4-tert-butylphenyl group can effectively suppress intermolecular π-π stacking, which is favorable for sublimation purification. Compared with Pt1, Pt4 has a trimethylphenyl group introduced into the quinoline part, which has a small effect on the HOMO and LUMO, and the change in ΔE is also small, so it is speculated that the change in the spectrum is small. This is thought to be due to the large dihedral angle and the breakage of the conjugated system.

[0136] figure 6As can be seen from the figure, in comparison with Pt1, Pt5 has a t-butyl group introduced into the quinoline moiety, and although an electron-donating group has been introduced, the effect on the LUMO is small, so even if an electron-withdrawing group is introduced into the quinoline moiety, the effect on the electron distribution (electron cloud) of the molecule is small, and it can be seen that the intermolecular π-π stacking can be suppressed by introducing an electron-donating group with large steric hindrance in that region. In comparison with Pt1, it can be clearly observed that the LUMO of Pt6 is significantly lowered. This is because the LUMO is mainly distributed in the quinoline moiety, and the LUMO distribution can be significantly lowered by introducing an electron-withdrawing group, a trifluoromethyl group, into the quinoline moiety, so the LUMO can be efficiently controlled by introducing an electron-withdrawing group at that position, and thereby the photophysical properties of the molecule can be controlled. In comparison with Pt1, in Pt7, a phenyl group has been introduced to the right side of the quinoline to increase the conjugated system, and it can be clearly observed that the HOMO of that part is dispersed on the phenyl group, and ΔE is reduced, which is presumed to cause a red shift in the emission spectrum. In comparison with Pt1, Pt8 links the acridine group and the quinoline group via a phenyl group, distributing the HOMO mainly in the quinoline moiety, and it is presumed that the LUMO is delocalized between the phenyl group and the quinoline moiety, decreasing ΔE and causing a red shift in the emission spectrum.

[0137] figure 7As can be seen from the figure, in comparison with Pt1, Pt9 has its LUMO portion distributed on the pyridine ring, but by introducing an electron-withdrawing group, trifluoromethyl group, on the pyridine, the LUMO distribution is delocalized in the direction of the pyridine ring, and the LUMO distribution is mainly distributed in the pyridine portion, with little effect on the HOMO distribution, and ΔE is lowered, which is presumed to red-shift the emission spectrum. In comparison with Pt1, Pt10 has a nitrogen atom that is an electron-withdrawing group like the trifluoromethyl group, so its LUMO is also delocalized in the pyridine portion like Pt9, and it is clearly observed that E is lowered, which is presumed to red-shift the emission spectrum. In comparison with Pt1, Pt11 has a nitrogen atom introduced into the quinoline portion, and its LUMO is delocalized in the quinoline portion, and it is clearly observed that the LUMO is lowered, which is presumed to red-shift the emission spectrum. Pt 12 shows similar results.

[0138] figure 8 As can be seen from the graph, in comparison with Pt1, Pt13 has increased the energy levels of the LUMO and HOMO without changing the energy band, and can be combined with a more suitable host material in the device. In comparison with Pt2, Pt14 has an increased conjugated system due to the introduction of a phenyl group, which causes delocalization in the HOMO, and the change in ΔE is small. In comparison with Pt3, Pt15 has one phenyl group introduced into the quinoline moiety and a t-butyl group introduced into the pyridine moiety, and except for the phenyl group bringing about a certain conjugated delocalization effect on the HOMO, there is no change in the HOMO and ΔE. LUMOIt can be observed that the effect on the electron distribution is small, so by introducing a t-butyl group into the pyridine ring, the steric hindrance in the space can be effectively increased and the effect on the electron density distribution (electron cloud) can be reduced, and the utilization efficiency of the excitons can be improved. By introducing a conjugated system into the quinoline region, the rigidity of the molecule can be increased and the effect on the electron distribution (electron cloud) is small. In comparison with Pt4, Pt16 has one t-butyl group introduced into each of the quinoline and pyridine parts, and the t-butyl group on the pyridine ring has a small effect on the electron distribution (electron cloud) and increases the steric hindrance in the space, which is advantageous for increasing the utilization efficiency of excitons. From the electron density distribution (electron cloud), it was observed that the t-butyl group on the quinoline side has a small effect on the distribution, so the change in the properties of the spectrum is small, and the structure of the two t-butyl groups is more advantageous for increasing the utilization efficiency of excitons.

[0139] figure 9 As can be seen from the figure, in comparison with Pt5, in Pt17, as can be seen from comparing Pt2 with Pt1, the introduction of a methyl group into the pyridine ring has a small effect on the electron distribution (electron cloud), and since the oxygen atom is replaced by a sulfur atom and the electron-withdrawing power of the sulfur atom is stronger than that of oxygen, its HOMO is delocalized at the sulfur atom, ΔE is lowered, and it is presumed that this causes a red shift in the emission spectrum. In comparison with Pt1, in Pt18, the oxygen atom is replaced by aniline, the dihedral angle of the conjugated plane of the phenyl group and quinoline is large, the conjugated system is broken, and the rigidity of the molecule is increased. The electron-donating group is HOMO It is speculated that the emission spectrum is red-shifted because the dihedral angles between the phenyl group and the 4-tert-butylphenyl group and the conjugated plane are large in Pt19 compared to Pt17, and the conjugated system is broken, so the HOMO, LUMOIt has a small effect on the electron distribution. In addition, it has been proven that the t-butyl group on the pyridine ring has a small effect on the electron distribution (electron cloud), so by introducing a t-butyl group on the pyridine ring and a 4-tert-butylphenyl group on the quinoline ring, the steric hindrance effect of the space can be increased, which is advantageous for suppressing intermolecular π-π stacking. Compared to Pt16, Pt20 has a diphenylamine, which is a strong electron donating group, and the HOMO energy level is significantly increased and ΔE is decreased, which can significantly red-shift the emission spectrum, thereby providing a significant effect in adjusting the emission color.

[0140] figure 10 As can be seen from the electron density distribution (electron cloud) of Pt1 in comparison with Pt1, the HOMO of Pt21, Pt22, Pt23, and Pt24 is distributed mainly within the quinoline conjugated system near the metallic Pt atom, and the LUMO is distributed mainly between the pyridine ring and the quinoline conjugated system. The bridge position of the 6-membered ring has little effect on the HOMO and LUMO, so Pt21 to Pt24 have less effect on controlling the molecular electron distribution (electron cloud) compared to Pt1.

[0141] In summary, the introduction of a strong electron-withdrawing structure at the oxygen para-position in the quinoline ring can significantly lower the energy level of the LUMO. The introduction of a strong electron-withdrawing structure in the pyridine ring can lower the energy level of the LUMO. The introduction of a 4-tert-butylphenyl group or a trimethylphenyl group at the oxygen para-position in the quinoline ring can suppress the π-π stacking of the molecule under conditions where the effect on the HOMO and LUMO is small, which is advantageous for the purification of the material molecule. The appropriate increase in the conjugated structure in the quinoline ring can increase the rigidity of the molecule and extend the conjugated system, thereby adjusting its photophysical properties.

[0142] The present invention relates to the use of the platinum (II) and palladium (II) complex luminescent material containing the quinoline structural unit described in the present invention in the luminescent layer of an organic electroluminescent device. In an organic light-emitting device, carriers are injected into the luminescent material from both the positive and negative electrodes, generating an excited luminescent material to emit light. The compound of the present invention represented by the general formula (1) can be used as a luminescent material in an organic light-emitting device such as an organic photoluminescent device or an organic electroluminescent device. The organic photoluminescent device has a structure in which at least a luminescent layer is formed on a substrate. The organic electroluminescent device has a structure in which at least an anode, a cathode, and an organic layer between the anode and the cathode are formed. The organic layer includes at least a luminescent layer, and may be composed of only the luminescent layer, or may have one or more organic layers in addition to the luminescent layer. Examples of the other organic layers include a hole transport layer, a hole injection layer, an electron barrier layer, a hole barrier layer, an electron injection layer, an electron transport layer, an exciton barrier layer, and the like. The hole transport layer may be a hole injection transport layer having a hole injection function, and the electron transport layer may be an electron injection transport layer having an electron injection function. The specific structural concept of the organic light-emitting device is shown in Figure 1. 13 As shown in the figure. 13 There are seven layers in total, from the middle to the top, which represent, in that order, the substrate, anode, hole injection layer, hole transport layer, light-emitting layer, electron transport layer, and cathode. Of these, the light-emitting layer is a mixed layer in which a host material is doped with a guest material.

[0143] The complexes shown in Examples 1 to 3 are used as phosphorescent light-emitting materials in OLED devices, and the structures are represented as follows:

[0144] ITO / HATCN (10 nm) / NPD (65 nm) / mCBP: Complexes shown in Examples 1 to 3 (5-20 wt.%, 20 nm) / BAlq (10 nm) / BPyTP (30 nm) / LiF (1 nm) / Al (100 nm)

[0145] Here, ITO is a transparent anode, HATCN is a hole injection layer, NPD is a hole transport layer, mCBP is a host material, the complexes shown in Examples 1 to 3 (5-20 wt.% is the doping concentration, and 20 nm is the thickness of the light-emitting layer) are guest materials, BAlq is a hole barrier layer, BPyTP is an electron transport layer, LiF is an electron injection layer, and Al is an anode. The number in parentheses in nanometers (nm) is the thickness of the thin film.

[0146] The above-mentioned structure is an application example of the light-emitting material in the present invention, and does not limit the specific OLED device structure of the light-emitting material shown in the present invention, and the light-emitting material is also not limited to the compounds shown in Examples 1 to 3.

[0147] The molecular formula of the material used in the device is:

[0148] [ka]

[0149] The characteristics of the OLED device based on the above device embodiment, such as external quantum efficiency (EQE), driving voltage, and lifetime, are shown in the following table. 2 As shown in.

[0150] [Table 2]

[0151] The above-mentioned embodiments are specific examples of the present invention, and those skilled in the art will understand that various changes in form and details may be made in actual use without departing from the spirit and scope of the present invention. For example, many of the substituent structures described herein may be replaced with other structures without departing from the spirit of the present invention.

[0152] (Additional Note) (Appendix 1) Having a structure represented by general formula (I): 1. A platinum(II) and palladium(II) complex containing a quinoline structural unit, characterized in that: [ka] During the ceremony, M is selected from Pt or Pd; A is O, S or NR 6 is selected from X is O, S, CH 2 , C.H.D., C.D. 2 , C.R. 7 R 8 , C=O, SiR 9 R 10 , N.H., N.D., N.R. 11 , P.H., P.D., P.R. 12 , R 13 P=O, S=O, or SO 2 Well, X is O, S or NR 14 is selected from Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Y 13 and Y 14 are each independently N or CH; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 each independently represents a mono-, di-, tri-, tetra- or unsubstituted group; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 each independently represents hydrogen, deuterium, an alkyl group, a halogenated alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, a heteroaryl group, an aryloxy group, a halogen, a cycloalkenyl group, a heterocyclyl group, an alkenyl group, an alkynyl group, a 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 ester group, a nitrile group, an isonitrile group, an alkoxycarbonyl group, an acylamino 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 phosphoramide group, an imino group, a sulfo group, a carboxyl group, a hydrazino group, a silyl group, a substituted silyl group, a polymerizable group, or a combination thereof, and two or more adjacent R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 can optionally be connected to form a fused ring.

[0153] (Appendix 2) The platinum complex has a structure represented by general formula (II), (III), (IV) or (V): 2. A platinum(II) and palladium(II) complex containing a quinoline structural unit according to claim 1. [ka]

[0154] (Appendix 3) Below on the left: [ka] is preferably any one selected from the following structures: 2. A platinum(II) and palladium(II) complex containing a quinoline structural unit according to claim 1. [ka]

[0155] (Appendix 4) The platinum(II) and palladium(II) complexes have any one of the following structures: 2. A platinum(II) and palladium(II) complex containing a quinoline structural unit according to claim 1. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0156] (Appendix 5) Use of a platinum(II) or palladium(II) complex containing a quinoline structural unit according to any one of claims 1 to 4 in an electroluminescent device.

[0157] (Appendix 6) A platinum (II) or palladium (II) complex containing a quinoline structural unit according to any one of claims 1 to 4, A device characterized in that

[0158] (Appendix 7) the device is a full color display, a photovoltaic device, an emissive display or an organic light emitting diode; 7. The device of claim 6.

[0159] (Appendix 8) At least one cathode, at least one anode, and at least one light-emitting layer, at least one of the light-emitting layers containing a platinum (II) or palladium (II) complex containing a quinoline structural unit according to any one of Supplementary Notes 1 to 4. 7. The device of claim 6.

[0160] (Appendix 9) The device is an organic light-emitting diode, and the light-emitting layer thereof comprises a platinum(II) or palladium(II) complex containing the quinoline structural unit and a corresponding host material, wherein the mass percentage of the platinum(II) or palladium(II) complex is 1%-50%, and the host material is not limited; 7. The device of claim 6.

[0161] (Appendix 10) Including a device according to any one of appendices 6 to 9, A display device or lighting device characterized by the above.

Claims

1. A compound having any one of the structures represented by the following formulas: A platinum(II) complex containing a quinoline structural unit, characterized in that: 【Chemistry 1】

2. 2. Use of a platinum(II) complex containing a quinoline structural unit according to claim 1 in an electroluminescent device.

3. The platinum (II) complex containing the quinoline structural unit according to claim 1 is included. A device characterized in that

4. the device is a full color display, a photovoltaic device, an emissive display or an organic light emitting diode; 4. The device according to claim 3 .

5. 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 platinum (II) complex containing a quinoline structural unit according to claim 1.

4. The device according to claim 3 .

6. The device is an organic light-emitting diode, and in its light-emitting layer, it comprises a platinum(II) complex containing the quinoline structural unit and a corresponding host material, where the mass percentage of the platinum(II) complex is 1%-50%, and the host material is not limited.

4. The device according to claim 3 .

7. 4. A device comprising: A display device or lighting device characterized by the above.

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