Metal platinum complex, organic optoelectronic device and display or lighting device

Abstract

The present invention provides a metal platinum complex, an organic optoelectronic device, and a display or lighting device. A new 6 / 5 / 7 metal ring structure is developed by using an 8-phenylquinoline structure and its derivatives, a benzo five-membered heterocycle, and a phenol oxygen tetradentate ligand to obtain a new type of tetradentate ring metal platinum complex phosphorescent material. The chemical formula of the phosphorescent material is shown in the general formula (1):

Description

Technical Field

[0001] The invention relates to a metal platinum complex, in particular to a metal platinum complex, an organic photoelectric device and a display or lighting device. Background Art

[0002] Organic Light-Emitting Diode (OLED) has made rapid progress in recent years. Compared with LCD display technology, OLED has the following advantages: self-luminescence, no need for backlight, energy saving; foldable or bendable; fast response speed, high contrast; wide operating temperature range; low material cost, high luminous efficiency, etc. OLED has become a new generation of full-color display and lighting technology, and has been widely valued by academia and industry. It has been widely used in flat panel display, solid lighting, military and aerospace fields, and is expected to replace liquid crystal display (LCD) in the future.

[0003] In the early stage of OLED development, traditional fluorescent materials were mainly used, which have good device stability. However, in theory, fluorescent materials can only utilize 25% of singlet excitons at most, and the remaining 75% of triplet excitons can only be deactivated by non-radiative transitions due to transition barriers, which limits their application in OLEDs. However, due to the spin-orbit coupling effect (SOC) of heavy metals, cyclometallated platinum complex phosphorescent materials can break the triplet transition barrier, effectively promote the intersystem hopping of electrons from singlet to triplet, and make full use of all singlet and triplet excitons generated by electroexcitation, so that their maximum theoretical quantum efficiency can reach 100%. Generally, the ligands of cyclometallated platinum complex phosphorescent materials include luminescent groups and auxiliary groups, and changes in their chemical structures will affect the electronic structure of the complex, and then affect its photophysical properties. Compared with bidentate and tridentate structures, tetradentate cyclometallic structures can effectively reduce vibration coupling, inhibit non-radiative attenuation, and help increase the radiation rate to achieve high quantum efficiency phosphorescent emission. Although tetradentate metal platinum complex phosphorescent materials have made great progress, stable and efficient platinum complex phosphorescent materials are still extremely limited. Therefore, the development of new tetradentate metal structure platinum complexes is still of great significance to the development of the OLED industry. Summary of the invention

[0004] In order to develop more types of higher performance phosphorescent materials, the object of the present invention is to provide a tetradentate metal platinum complex phosphorescent material and an organic light-emitting device based on 8-phenylquinoline derivatives.

[0005] The tetradentate metal platinum complex phosphorescent material provided by the present invention comprises a compound represented by the following general formula (1):

[0006]

[0007] in,

[0008] 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 , Y 14 , Y 15 and Y 16 are each independently CH or N;

[0009] R 1 , R 2 , R 3 , R 4 and R 5 Each independently represents mono-, di-, tri-, tetra- or unsubstituted, and R 1 , R 2 , R 3 , R 4 and R 5 R is independently hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, thiol, nitro, cyano, amino, mono- or di-alkylamino, mono- or di-arylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, urea, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, polymeric group, or a combination thereof; and two or more adjacent R 1 , R 2 , R 3 , R 4 and R 5 They are independent or selectively linked to form a fused ring.

[0010] X stands for NR a , O, S; among them, R arepresents hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, thiol, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, urea, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, polymeric group, or a combination thereof; and may be connected to adjacent R 3 and R 4 They are independent or selectively linked to form a fused ring.

[0011] Z stands for O, S, NR b ; Among them, R b represents hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, thiol, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, urea, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted silyl, polymeric group, or a combination thereof; and may be connected to adjacent R 1 and R 5 They are independent or selectively linked to form a fused ring.

[0012] Preferably, the phosphorescent material is any one of the following structural formulas:

[0013]

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023] The present invention provides an organic photoelectric device, comprising:

[0024] a first electrode;

[0025] a second electrode facing the first electrode;

[0026] an organic functional layer, which is sandwiched between the first electrode and the second electrode;

[0027] Wherein, the organic functional layer comprises the organic metal complex of the present invention.

[0028] The present invention provides an organic photoelectric device, which comprises a cathode layer, an anode layer and an organic layer, wherein the organic layer comprises at least one of a hole injection layer, a hole transport layer, a light-emitting layer or an active layer, an electron injection layer and an electron transport layer, wherein any layer of the device contains the organic metal complex of the present invention.

[0029] Preferably, the organic optoelectronic device is an organic photovoltaic device, an organic light-emitting device, an organic solar cell, electronic paper, an organic photoreceptor, an organic thin film transistor or an organic memory device, preferably an organic light-emitting diode device or a light-emitting electrochemical cell.

[0030] Preferably, the light-emitting layer contains the organic metal complex and a corresponding host material, wherein the mass percentage of the organic metal complex is between 1% and 50%.

[0031] The present invention further provides an organic light-emitting device, which has a light-emitting layer containing the metal platinum complex of the present invention on a substrate.

[0032] The present invention further provides a device, which comprises the metal platinum complex of the present invention.

[0033] Preferably, the device is a full-color display, a photovoltaic device, a light-emitting display device or an organic light-emitting diode.

[0034] Preferably, it comprises at least one cathode, at least one anode and at least one light-emitting layer, at least one of the light-emitting layers comprises the metal platinum complex of the present invention.

[0035] Preferably, the device is an organic light emitting diode, the light emitting layer of which contains the metal platinum complex and a corresponding host material, wherein the mass percentage of the metal platinum complex is between 1% and 50%, and the host material has no restrictions. The present invention also provides the use of the organic metal complex in the manufacture of an organic optoelectronic device.

[0036] The present invention further provides a display or lighting device comprising the organic optoelectronic device of the present invention.

[0037] Preferably, the tetradentate metal platinum complex phosphorescent material based on 8-phenylquinoline derivatives is used in an organic light-emitting device, wherein the organic light-emitting device is an organic light-emitting diode, a light-emitting diode or a light-emitting electrochemical cell.

[0038] Compared with the prior art, the present invention develops a new 6 / 5 / 7 metal ring structure by using 8-phenylquinoline and its derivatives, benzo five-membered heterocyclic ring and phenol oxygen tetradentate ligand to obtain a new type of tetradentate ring metal platinum complex phosphorescent material. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is an emission spectrum of the metal platinum (II) phosphorescent luminescent material in Example 1 of the present invention in a deoxygenated state in a dichloromethane solution at room temperature;

[0040] Figure 2 ab are schematic diagrams of HOMO and LUMO orbital distribution of compound Pt-1;

[0041] Figure 3 ab are schematic diagrams of HOMO and LUMO orbital distribution of compound Pt-77;

[0042] Figure 4 ab are schematic diagrams of HOMO and LUMO orbital distribution of compound Pt-49, respectively;

[0043] Figure 5 ab are schematic diagrams of HOMO and LUMO orbital distribution of compound Pt-61;

[0044] Figure 6 ab are schematic diagrams of HOMO and LUMO orbital distribution of compound Pt-79 respectively;

[0045] Figure 7 ab are schematic diagrams of HOMO and LUMO orbital distribution of compound Pt-80 respectively;

[0046] Figure 8 ab are schematic diagrams of HOMO and LUMO orbital distribution of compound Pt-101;

[0047] Fig. 9 ab are schematic diagrams of HOMO and LUMO orbital distribution of compound Pt-113;

[0048] Fig.10 ab are schematic diagrams of HOMO and LUMO orbital distribution of compound Pt-114;

[0049] Fig.11 It is a schematic structural diagram of the organic light-emitting device of the present invention. DETAILED DESCRIPTION

[0050] By reference to the following specific embodiments and the examples contained therein, the disclosure can be more easily understood. Before disclosing and describing the compounds, devices and / or methods of the present invention, it should be understood that, unless otherwise stated, they are not limited to specific synthetic methods or specific reagents, because this can be varied. It should also be understood that the terms used in the present invention are only used to describe specific aspects and are not intended to be limiting. Although any methods and materials similar or equivalent to those described in the present invention can be used in this practice or test, exemplary methods and materials are now described.

[0051] As used in the specification and the appended claims, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component" includes a mixture of two or more components.

[0052] As used herein, the terms "optional" or "optionally" mean 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.

[0053] Disclosed are components that can be used to prepare the compositions described herein, as well as the compositions themselves to be used in the methods disclosed in the present invention. The present invention discloses these and other materials, and it should be understood that combinations, subsets, interactions, groups, etc. of these substances are disclosed, and although specific references to each different individual and total combination and arrangement of these compounds cannot be specifically disclosed, each has a special concept and description. For example, if a specific compound is disclosed and discussed, and many modifications that can be made to many molecules containing the compound are discussed, then each combination and arrangement of the compound and possible modifications are specifically considered, unless the opposite possible modification is specifically indicated. Therefore, if a class of molecules A, B and C and a class of molecules D, E and F are disclosed, and an example of a combination molecule AD, then even if each is not recorded individually, each individual and total meaning combination, AE, AF, BD, BE, BF, CD, CE and CF are also considered to be disclosed. Similarly, any subset or combination of these is also disclosed. For example, subgroups of AE, BF and CE are also disclosed. This concept applies to all aspects of the present invention, including but not limited to steps in the method of preparing and using the composition. Thus, if there are a variety of additional steps that can be performed, it should be understood that each of these additional steps can be performed with a specific embodiment or combination of embodiments of the method.

[0054] The connecting atom used in the present invention can connect two groups, for example, connecting N and C. The connecting atom can optionally (if valence bonds allow) attach other chemical groups. For example, an oxygen atom will not have any other chemical groups attached, because once the two atoms (for example, N or C) are bonded, the valence bonds are satisfied. On the contrary, when carbon is the connecting atom, two additional chemical groups can be attached to the carbon atom. Suitable chemical groups include, but are not limited to, hydrogen, hydroxyl, alkyl, alkoxy, =O, halogen, nitro, amine, amide, sulfhydryl, aryl, heteroaryl, cycloalkyl and heterocyclic radicals.

[0055] As used herein, the term "cyclic structure" or similar terms refers to any cyclic chemical structure, including but not limited to aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclic carbene.

[0056] The term "substituted" or similar terms used in the present invention include all allowed substituents of organic compounds. In a broad sense, allowed substituents include cyclic and non-cyclic, branched and non-branched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds. For example, exemplary substituents include the following. For suitable organic compounds, allowed substituents may be one or more, the same or different. For the purposes of the present invention, heteroatoms (such as nitrogen) can have hydrogen substituents and / or any allowed substituents of organic compounds that meet the heteroatom valence bonds described in the present invention. The present invention is not intended to impose any restrictions in any way with allowed substituents of organic compounds. Similarly, the term "substituted" or "substituted with" includes implicit conditions that such substitutions conform to the allowed valence bonds of the substituted atom and the substituent, and the substitution results in a stable compound (e.g., a compound that will not spontaneously undergo transformation (e.g., by rearrangement, cyclization, elimination, etc.)). In some aspects, unless explicitly stated to the contrary, a single substituent can be further optionally substituted (i.e., further substituted or unsubstituted).

[0057] In defining various terms, “R 1 ”, “R 2 ”, “R 3 ” and “R 4 " are used as general symbols in the present invention to represent various specific substituents. These symbols can be any substituents, not limited to those disclosed in the present invention, and when they are defined as certain substituents in one example, they may also be defined as some other substituents in another example.

[0058] The term "alkyl" used in the present invention is a saturated hydrocarbon group of 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group can be cyclic or non-cyclic. The alkyl group can be branched or non-branched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can replace one or more groups, including but not limited to the alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxyl, nitro, silyl, sulfur-oxo group and mercapto group optionally substituted according to the present invention. A "low alkyl" group is an alkyl group containing 1 to 6 (e.g., 1 to 4) carbon atoms.

[0059] Throughout the specification, "alkyl" generally refers to both unsubstituted alkyl and substituted alkyl; however, substituted alkyl is also specifically referred to in the present invention by identifying the specific substituents on the alkyl. 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 substituted with one or more alkoxy groups, as described below. The term "alkylamino" specifically refers to an alkyl substituted with one or more amino groups, as described below, etc. When "alkyl" is used in one context and a specific term such as "alkyl alcohol" is used in another context, it is not meant to imply that the term "alkyl" does not also refer to a specific term such as "alkyl alcohol", etc.

[0060] This approach also applies to 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 moieties may be specifically identified in the present invention; for example, a specific substituted cycloalkyl may be referred to as, for example, "alkylcycloalkyl". Similarly, a substituted alkoxy may be specifically referred to as, for example, "haloalkoxy", and a specific substituted alkenyl may be, for example, "enol", etc. Similarly, the use of a general term such as "cycloalkyl" and a specific term such as "alkylcycloalkyl" does not mean that the general term does not also include the specific term.

[0061] The term "cycloalkyl" used in the present invention is a non-aromatic carbonyl ring of 3 to 30 carbon atoms consisting of at least three carbon atoms. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, etc. The term "heterocycloalkyl" is a class of cycloalkyl as defined above, and is included in the meaning of the term "cycloalkyl", wherein at least one ring carbon atom is replaced by a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur or phosphorus. The cycloalkyl and heterocycloalkyl may be substituted or unsubstituted. The cycloalkyl and heterocycloalkyl may be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxyl, nitro, silyl, sulfur-oxo group and mercapto as described in the present invention.

[0062] The term "polyolefin group" used in the present invention refers to a group containing two or more CH2 groups connected to each other. The "polyolefin group" can be represented by -(CH2) a —, where “a” is an integer between 2 and 500.

[0063] The terms "alkoxy" and "alkoxy group" used in the present invention refer to an alkyl or cycloalkyl group of 1 to 30 carbon atoms bonded through an ether bond; that is, "alkoxy" can be defined as -OR 1 , where R 1 is an alkyl or cycloalkyl group as defined above. "Alkoxy" also includes the alkoxy polymers just described; that is, the alkoxy group may be a polyether, such as -OR 1 -OR 2 OR 1 -(OR 2 ) a -OR 3 , where "a" is an integer from 1 to 500, and R 1 , R 2 and R 3 Each is independently an alkyl group, a cycloalkyl group or a combination thereof.

[0064] 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. 1 R 2 )C=C(R 3 R 4 ) includes E and Z isomers. This can be inferred in the structural formula of the present invention where an asymmetric olefin is present, or it can be explicitly indicated by the bond symbol C=C. The alkenyl group can be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo or thiol as described herein.

[0065] The term "cycloalkenyl" used in the present invention is a non-aromatic carbonyl ring of 3 to 30 carbon atoms, which is composed of at least 3 carbon atoms and contains at least one carbon-carbon double bond, i.e., C=C. Examples of cycloalkenyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, etc. The term "heterocycloalkenyl" is a class of cycloalkenyls as defined above and is included in the meaning of the term "cycloalkenyl", wherein 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 may be substituted or unsubstituted. The cycloalkenyl and heterocycloalkenyl may be substituted with one or more groups, including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, sulfur-oxo or sulfhydryl as described in the present invention.

[0066] The term "alkynyl" as used herein is a hydrocarbon group having 2 to 30 carbon atoms, the structural formula of which contains 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, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, thio-oxo or thiol as described herein.

[0067] The term "cycloalkynyl" used in the present invention is a non-aromatic carbonyl ring comprising at least 7 carbon atoms and containing at least one carbon-carbon triple bond. Examples of cycloalkynyl include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, etc. The term "heterocycloalkynyl" is a cycloalkenyl as defined above, and is included in the meaning of the term "cycloalkynyl", wherein at least one of the carbon atoms of the ring is replaced by a heteroatom, such as, but not limited to, nitrogen, oxygen, sulfur or phosphorus. Cycloalkynyl and heterocycloalkynyl may be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl may be substituted with one or more groups, including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, sulfur-oxo or sulfhydryl groups described in the present invention.

[0068] The term "aryl" used in the present invention refers to a group containing 60 carbon atoms or less of any carbon-based aromatic, including but not limited to benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, etc. The term "aryl" also includes "heteroaryl", which is defined as a group containing aromatics, and the aromatic group contains at least one heteroatom in the ring. Examples of heteroatoms include but are not limited to nitrogen, oxygen, sulfur or phosphorus. Similarly, the term "non-heteroaryl" (which is also included in the term "aryl") defines a group containing aromatics, and the aromatic group does not contain heteroatoms. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with one or more groups, and the groups include but are not limited to alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silyl, sulfur-oxo group or sulfhydryl described in the present invention. The term "biaryl" is a specific type of aryl and is included in the definition of "aryl". Biaryl refers to two aryl groups bound together via a fused ring structure, as in naphthalene, or connected via one or more carbon-carbon bonds, as in biphenyl.

[0069] The term "aldehyde" used in the present invention is represented by the formula - C(O)H. Throughout the specification, "C(O)" is a short form of carbonyl (ie, C=O).

[0070] The term "amine" or "amino" as used herein refers to an amino group having the formula: NR 1 R 2 Indicates that R 1 and R 2 The radicals may be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl.

[0071] 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-butylamino, tert-butylamino, pentylamino, isopentylamino, tert-pentylamino, hexylamino, and the like.

[0072] The term "dialkylamino" as used herein is represented by the formula -N(-alkyl)2, wherein the alkyl group is as described herein. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di-sec-butylamino, di-tert-butylamino, dipentylamino, diisopentylamino, di-tert-pentylamino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino, and the like.

[0073] The term "carboxylic acid" as used herein is represented by the formula -C(O)OH.

[0074] The term "ester" as used herein refers to a 1 Or—C(O)OR 1 Indicates that R 1 It can be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described in the present invention. The term "polyester" used in the present invention is represented by the formula: (R 1 O(O)CR 2 -C(O)O) a —or—(R 1 O(O)CR 2 -OC(O)) a — indicates that R 1 and R 2 It can be independently an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described in the present invention 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.

[0075] The term "ether" as used herein refers to 1 OR 2 Indicates that R 1 and R 2 The term "polyether" as used in the present invention is represented by the formula: (R 1 OR 2 O) a — indicates that R 1 and R 2 It may be independently an alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, aryl group or heteroaryl group as described in the present invention and "a" is an integer from 1 to 500. Examples of the polyether group include polyethylene oxide, polypropylene oxide and polybutylene oxide.

[0076] The term "halogen" as used herein refers to the halogens fluorine, chlorine, bromine and iodine.

[0077] The term "heterocyclyl" as used herein refers to monocyclic and polycyclic non-aromatic ring systems, and "heteroaryl" as used herein refers to monocyclic and polycyclic aromatic ring systems of no more than 60 carbon atoms: wherein at least one of the ring members is not carbon. The term includes azetidinyl, dioxanyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl (including 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl and 1,3,4-oxadiazolyl oxazolyl), piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, including 1,2,4, tetrazinyl including 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.

[0078] The term "hydroxyl" as used herein is represented by the formula -OH.

[0079] The term "ketone" as used herein refers to 1 C(O)R 2 Indicates that R 1 and R 2 They may independently be the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl groups described in the present invention.

[0080] The term "azido" used in the present invention is represented by the formula -N3.

[0081] The term "nitro" as used herein is represented by the formula -NO2.

[0082] The term "nitrile" as used herein is represented by the formula -CN.

[0083] The term "silyl" as used herein refers to a group having the formula: SiR 1 R 2 R 3 Indicates that R 1 , R 2 and R 3 It may independently be hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described in the present invention.

[0084] The term "sulfur-oxo group" as used herein is represented by the formula: S(O)R 1 ,—S(O)2R 1 ,—OS(O)2R 1 OR—OS(O)2OR1 Indicates that R 1 It can be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described in the present invention. Throughout the specification, "S(O)" is a short form of S=O. The term "sulfonyl" used in the present invention refers to a sulfonyl group represented by the formula: S(O)2R 1 A thio-oxo group represented by 1 It can be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl. The term "sulfone" as used herein refers to a radical of the formula R 1 S(O)2R 2 Indicates that R 1 and R 2 The term "sulfoxide" used in the present invention is represented by the formula R 1 S(O)R 2 Indicates that R 1 and R 2 They may independently be the alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl groups described in the present invention.

[0085] The term "mercapto" as used herein is represented by the formula -SH.

[0086] The "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 For example, if the first group is a straight chain alkyl, one of the hydrogen atoms of the alkyl group may be optionally substituted with a hydroxyl, an alkoxy, an alkyl group, a halogen, etc. Depending on the selected group, the first group may be incorporated into the second group, or the first group may be side-linked (i.e., connected) to the second group. For example, for the phrase "an alkyl group containing an amino group", the amino group may be incorporated into the main chain of the alkyl group. Alternatively, the amino group may be connected to the main chain of the alkyl group. The nature of the selected group will determine whether the first group is embedded in or connected to the second group.

[0087] The compounds of the present invention may contain "optionally substituted" parts. Generally, the term "substituted" (whether or not the term "optionally" is present in front) means that one or more hydrogens of the specified part are replaced by suitable substituents. Unless otherwise specified, the "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure can be substituted by more than one substituent selected from the specified group, the substituent may be the same or different at each position. The substituent combination envisioned by the present invention is preferably a combination of stable or chemically feasible compounds. It can also be envisioned that, in some aspects, unless explicitly stated to the contrary, each substituent may be further optionally substituted (that is, further substituted or unsubstituted).

[0088] The structure of the compound can be represented by the following formula:

[0089]

[0090] It is understood to be equivalent to the following formula:

[0091]

[0092] Where n is usually an integer. That is, R n is understood to mean five individual substituents R n(a) , R n(b) , R n(c) , R n(d) , R n (e) "Individual substituent" means that each R substituent can be defined independently. For example, if in one case R n(a) is a halogen, then in this case R n(b) Not necessarily halogen.

[0093] In the chemical structures and units disclosed and described in the present invention, R is mentioned several times. 1 , R 2 , R 3 , R 4 , R 5 , R 6 In the manual R 1 , R 2 , R 3 , R 4 , R 5 , R 6 Any description of etc. applies to reference R 1 , R 2 , R 3 , R 4 , R 5 , R 6 Unless otherwise specified, any structure or unit of the present invention is not limited to:

[0094] Optoelectronic devices using organic materials are becoming increasingly desirable for a variety of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic optoelectronic devices have the potential to outperform inorganic devices in terms of cost. In addition, the inherent properties of organic materials, such as their flexibility, can make them well suited for special 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 often be easily tuned with appropriate dopants.

[0095] Excitons decay from singlet excited states to the ground state to produce instant luminescence, which is fluorescence. If excitons decay from triplet excited states to the ground state to produce luminescence, this is phosphorescence. Due to the strong spin-orbit coupling between singlet and triplet excited states of heavy metal atoms, intersystem crossing (ISC) is effectively enhanced, so phosphorescent metal complexes (such as platinum complexes) have shown their potential to simultaneously utilize singlet and triplet excitons to achieve 100% internal quantum efficiency. Therefore, phosphorescent metal complexes are good candidates for dopants in the emission layer of organic light-emitting devices (OLEDs) and have received great attention in academic and industrial fields. In the past decade, many achievements have been made, leading to the profitable commercialization of this technology, for example, OLEDs have been used in advanced displays for smartphones, TVs, and digital cameras.

[0096] However, blue electroluminescent devices remain the most challenging area of ​​the technology to date, with stability of blue devices being a major issue. It has been shown that the choice of host material is very important for the stability of blue devices. However, the triplet excited state (T1) minimum energy of blue emitting materials is very high, which means that the triplet excited state (T1) minimum energy of the host material of blue devices should be higher. This makes the development of host materials for blue devices more difficult.

[0097] The metal complexes of the present invention can be customized or tuned to specific applications where specific emission or absorption characteristics are desired. The optical properties of the metal complexes in the present disclosure can be adjusted by changing the structure of the ligands surrounding the metal center or by changing the structure of the fluorescent emitters on the ligands. For example, metal complexes with ligands that have electron-donating substituents or electron-withdrawing substituents can generally exhibit different optical properties in emission and absorption spectra. The color of the metal complex can be adjusted by modifying the conjugated groups on the fluorescent emitters and ligands.

[0098] The emission of such complexes of the present invention can be adjusted, for example, from ultraviolet to near infrared by changing the structure of the ligand or fluorescent emitter. A fluorescent emitter is a group of atoms in an organic molecule that can absorb energy to produce a singlet excited state, and the singlet exciton decays rapidly to produce instant luminescence. On the one hand, the complexes of the present invention can provide emission of most of the visible spectrum. In a specific example, the complexes of the present invention can emit light in the range of about 400nm to about 700nm. On the other hand, the complexes of the present invention have improved stability and efficiency relative to traditional emission complexes. In addition, the complexes of the present invention can be used as luminescent markers of emitters or combinations thereof in, for example, biological applications, anticancer agents, organic light emitting diodes (OLEDs). On the other hand, 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.

[0099] Disclosed herein are compounds or complexes containing platinum. The terms compound or complex are used interchangeably in the present invention. In addition, the compounds disclosed herein have a neutral charge.

[0100] The compounds disclosed herein can exhibit desirable properties and have emission and / or absorption spectra that can be tuned by selecting appropriate ligands. In another aspect, the invention can exclude any one or more compounds, structures or portions thereof specifically recited herein.

[0101] 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 markers for biological applications.

[0102] 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.

[0103] The compounds disclosed herein can be used in various applications. As luminescent materials, the compounds can be used in organic light emitting diodes (OLEDs), light emitting devices and displays, and other light emitting devices.

[0104] 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.

[0105] The compounds disclosed herein can 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 phosphorescence emitters. In another aspect, the compounds disclosed herein can be delayed fluorescence emitters and phosphorescence emitters.

[0106] The contents of the present invention will be described in detail below. The description of the constituent elements described below may be based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples.

[0107] The present disclosure relates to cyclometallated platinum complexes, which can be used as light-emitting materials and host materials in OLED devices.

[0108] The following examples provide those of ordinary skill in the art with information on how to make and evaluate the compounds and OLED devices described in the present invention, which are exemplary of the present disclosure and are not intended to limit the scope thereof. Although every effort has been made to ensure the accuracy of the values ​​(e.g., amounts, temperatures, etc.), some errors and deviations should be considered. Unless otherwise stated, temperatures are in ° C. or at ambient temperature, and pressures are at or near atmospheric pressure.

[0109] The preparation method for the disclosed compound described in the present embodiment is one of many methods. There are many other methods for the preparation method of the disclosed compound in the present application, and the present application does not limit the scope. Therefore, the technicians in the field of the present disclosure can easily modify the described method or use different methods to prepare one or more of the disclosed compounds. The following methods are only exemplary, and the temperature, catalyst, concentration, reactant composition, and other process conditions can be changed, and for the desired compound, the technicians in the field of the present disclosure can easily select suitable reactants and conditions for preparation.

[0110] Unless otherwise stated, all commercial reagents involved in the following experiments were used directly after purchase without further purification. Both hydrogen and carbon nuclear magnetic resonance spectra were measured in deuterated chloroform (CDCl3) or deuterated dimethyl sulfoxide (DMSO-d6) solutions. The hydrogen spectrum used a 400 or 500 MHz nuclear magnetic resonance spectrometer, and the chemical shift was based on the residual solvent. If CDCl3 is used as the solvent, the hydrogen spectrum uses CDCl3 (δ = 7.26ppm) as the internal standard. If DMSO-d6 is used as the solvent, the hydrogen spectrum DMSO-d6 (δ = 2.50ppm) is used as the internal standard. The following abbreviations (or combinations) are used to explain hydrogen spectrum peaks: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad peak.

[0111] Example 1: Synthesis of Tetradentate Metal Platinum (II) Complex Pt-17:

[0112]

[0113] (1) Synthesis of intermediate QL-CHO: tBuQL-Br (2.0 g, 7.57 mmol, 1.0 equivalent), 3-formylphenylboronic acid (1.36 g, 9.09 mmol, 1.2 equivalent), tetrakistriphenylphosphine palladium (175 mg, 0.15 mmol, 2 mol%) and sodium carbonate (1.61 g, 15.14 mmol, 2.0 equivalent) were added to a 100 mL dry three-necked flask with a magnetic stirrer, and nitrogen was replaced three times. Toluene (12 mL), ethanol (10 mL) and water (5 mL) were added under nitrogen protection. The sealed tube was placed in an oil bath at 90°C with stirring, reacted for 58 hours, cooled to room temperature, washed with water, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 50:1-10:1, to obtain 1.97 mg of brown solid, with a yield of 90%. 1 HNMR (500MHz, CDCl3) δ1.47(s,9H),7.42(dd,J=8.0,4.0Hz,1H),7.67(t,J=7.5Hz,1H),7.79(d,J=2.0Hz,1H),7.83(d,J=2.0Hz,1H),7.94(dt, J=7.5,1.5Hz,1H),8.00(dt,J=7.5,1.5Hz,1H),8.20(dd,J=8.5,2.0Hz,1H),8.22(t,J=2.0Hz,1H),8.88(dd,J=4.0,2.0Hz,1H),10.12(s,1H).

[0114] (2) Synthesis of intermediate 1-Br: QL-CHO (314 mg, 1.08 mmol, 1.0 equivalent), NH2-Br (450 mg, 1.14 mmol, 1.05 equivalent), sodium metabisulfite (238 mg, 1.25 mmol, 1.1 equivalent) and N,N-dimethylformamide (6 mL) were added to a reaction tube equipped with a magnetic stirrer. The mixture was stirred in an oil bath at 90°C for 3 days, cooled to room temperature, diluted with ethyl acetate, and the organic phase was washed with water. After separation, the organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was distilled under reduced pressure to remove the solvent. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 50:1-10:1, to obtain 648 mg of a white solid, with a yield of 86%. 1HNMR(500MHz, CDCl3)δ1.29(s,9H),1.46(s,9H),6.66–6.68(m,2H),6.97–7.00(m,2H),7. 03–7.06(m,1H),7.09(t,J=8.0Hz,1H),7.19(dd,J=8.0,1.0Hz,1H),7.21(dt,J=8.0,1.5Hz ,1H),7.24–7.26(m,1H),7.35–7.38(m,2H),7.46–7.51(m,3H),7.54–7.55(m,1H),7.64–7. 66 (m, 2H), 7.71 (d, J = 2.5Hz, 1H), 8.14 (dd, J = 8.5, 2.0Hz, 1H), 8.83 (dd, J = 4.0, 2.0Hz, 1H).

[0115] (3) Synthesis of intermediate 1-OMe: 1-Br (640 mg, 0.96 mmol, 1.0 equivalent), 1-Bpin (359 mg, 1.16 mmol, 1.2 equivalent), tetrakistriphenylphosphine palladium (43 mg, 0.03 mmol, 3 mol%) and potassium carbonate (265 mg, 1.92 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor, and nitrogen was replaced three times. 1,4-dioxane (6 mL) and water (1 mL) were added under nitrogen protection. The sealed tube was placed in an oil bath at 85°C and stirred for 41 hours. The mixture was cooled to room temperature, washed with water, and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 50:1-7:1, to obtain 724 mg of a white solid with a yield of 98%. 1HNMR(500MHz, CDCl3)δ1.31(s,9H),1.42(s,9H),3.86(s,3H),6.66–6.68(m,2H),6.96–6.99(m,2H),7.02–7.0 6(m,1H),7.10(d,J=8.5Hz,1H),7.13(dt,J=8.0,1.5Hz,1H),7.19–7.25(m,2H),7.27–7.35(m,5H),7.39(d,J= 2.5Hz,1H),7.46(dd,J=7.0,1.5Hz,1H),7.49(t,J=2.0Hz,1H),7.54(ddd,J=15.0,8.5,2.5Hz,2H),7.58–7.63 (m,5H),7.69(d,J=2.5Hz,1H),7.92(d,J=2.5Hz,1H),8.12(dd,J=8.5,2.0Hz,1H),8.80(dd,J=4.0,2.0Hz,1H).

[0116] (4) Synthesis of ligand 1-OH: 1-OMe (700 mg, 0.91 mmol, 1.0 equivalent), pyridine hydrochloride (1.05 g, 9.11 mmol, 10 equivalents) and 1,3-dimethyl-2-imidazolidinone (3 mL) were added to the reaction tube in sequence. The nitrogen was replaced three times, and the mixture was placed in an oil bath at 180°C for 13 hours. The mixture was cooled to room temperature, quenched with sodium bicarbonate solution, extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 50:1-5:1, and 634 mg of white solid was obtained, with a yield of 92%. 1 HNMR(500MHz,DMSO-d6)δ1.18(s,9H),1.40(s,9H),6.66–6.69(m,2H),7.01–7.11(m,4H),7.2 2–7.27(m,3H),7.32–7.39(m,6H),7.48(dd,J=8.5,4.0Hz,1H),7.54(dd,J=8.5,2.5Hz,1H),7 .59(dd,J=8.5,2.5Hz,1H),7.61–7.65(m,5H),7.70(d,J=8.5Hz,1H),7.89(d,J=2.0Hz,1H),7 .96(d,J=2.5Hz,1H), 8.36(dd,J=8.5,2.0Hz,1H), 8.70(dd,J=4.0,2.0Hz,1H), 10.53(s,1H).

[0117] (5) Synthesis of Pt-17: 1-OH (150 mg, 0.2 mmol, 1.0 equivalent), potassium chloroplatinate (87 mg, 0.21 mmol, 1.05 equivalent), tetra-n-butylammonium bromide (6 mg, 0.02 mmol, 0.1 equivalent) were added to a 50 mL dry three-necked flask equipped with a magnetic rotor and a condenser. The nitrogen was replaced three times, and acetic acid (15 mL) was added. After nitrogen was bubbled through the reaction liquid for 30 minutes, the mixture was stirred at room temperature for 8 hours, and then reacted at 120°C for 60 hours. The mixture was cooled to room temperature and the solvent was removed by distillation under reduced pressure. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 1:1-0:1, to obtain 117 mg of a yellow solid product with a yield of 62%. 1 HNMR(500MHz,DMSO-d6)δ1.49(s,18H),6.56–6.58(m,1H),7.01(d,J=8.5Hz,1H),7.06(dd,J=8.0,1 .0Hz,1H),7.11–7.22(m,7H),7.34–7.43(m,5H),7.56–7.59(m,3H),7.76(d,J=2.5Hz,1H),7.78(d, J=8.5Hz,1H),7.84(dd,J=8.5,2.5Hz,1H),8.02(dd,J=8.0,5.5Hz,1H),8.06(d,J=8.0Hz,1H),8.16 (d, J=2.0Hz, 1H), 8.66 (d, J=2.5Hz, 1H), 8.96 (dd, J=8.5, 2.0Hz, 1H), 11.00 (dd, J=5.5, 1.5Hz, 1H).

[0118] Example 2: Synthesis of Tetradentate Metal Platinum (II) Complex Pt-18:

[0119]

[0120] (1) Synthesis of intermediate 2-OMe: 1-Br (1.0 equivalent), 2-Bpin (1.2 equivalent), tetrakistriphenylphosphine palladium (3 mol%) and potassium carbonate (2.0 equivalent) were added to a sealed tube with a magnetic rotor, and nitrogen was replaced three times. 1,4-dioxane (6 mL) and water (1 mL) were added under nitrogen protection. The sealed tube was placed in an oil bath at 85°C and stirred for 48 hours. The mixture was cooled to room temperature, washed with water, and extracted with ethyl acetate. The aqueous layer was extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 50:1-7:1, to obtain a white solid with a yield of about 90%. MS: molecular weight 781.37.

[0121] (2) Synthesis of ligand 2-OH: 2-OMe (1.0 equivalent), pyridine hydrochloride (10 equivalents) and 1,3-dimethyl-2-imidazolidinone (5 mL) were added to the reaction tube in sequence. The nitrogen was replaced three times, and the mixture was placed in an oil bath at 180°C for 11 hours, cooled to room temperature, quenched with sodium bicarbonate solution, extracted three times with ethyl acetate, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 50:1-5:1, to obtain a white solid with a yield of about 80%. MS: molecular weight 767.35.

[0122] (3) Synthesis of Pt-18: 2-OH (1.0 equivalent), potassium chloroplatinate (1.05 equivalent), tetrabutylammonium bromide (0.1 equivalent) were added to a dry three-necked flask with a magnetic rotor, nitrogen was replaced three times, acetic acid (25 mL) was added, and the reaction liquid was nitrogen bubbled for 30 minutes, stirred at room temperature for 12 hours, and then reacted at 120°C for 72 hours, cooled to room temperature, and the solvent was removed by vacuum distillation. The obtained crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 1:1-0:1, and the product was obtained as a yellow solid with a yield of about 50%. MS: molecular weight 960.30.

[0123] Example 3: Synthesis of Tetradentate Metal Platinum (II) Complex Pt-64:

[0124]

[0125] (1) Synthesis of intermediate 3-OMe: Add 3-Br (1.0 equivalent), 1-Bpin (1.2 equivalent), tetrakistriphenylphosphine palladium (3 mol%) and potassium carbonate (2.0 equivalent) to a sealed tube with a magnetic rotor, replace nitrogen three times, and add 1,4-dioxane (6 mL) and water (1 mL) under nitrogen protection. Place the sealed tube in an oil bath at 85°C and stir, react for 48 hours, cool to room temperature, wash with water, add ethyl acetate for extraction, extract the water layer with ethyl acetate three times, dry over anhydrous sodium sulfate, filter, and distill under reduced pressure to remove the solvent. The crude product is separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 50:1-7:1, to obtain a white solid with a yield of about 85%. MS: molecular weight 560.25.

[0126] (2) Synthesis of ligand 3-OH: 3-OMe (1.0 equivalent), pyridine hydrochloride (10 equivalents) and 1,3-dimethyl-2-imidazolidinone (6 mL) were added to the reaction tube in sequence. The nitrogen was replaced three times, and the mixture was placed in an oil bath at 180°C for 10 hours, cooled to room temperature, quenched with sodium bicarbonate solution, extracted three times with ethyl acetate, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 50:1-5:1, to obtain a white solid with a yield of about 85%. MS: molecular weight 546.23.

[0127] (3) Synthesis of Pt-64: 3-OH (1.0 equivalent), potassium chloroplatinate (1.05 equivalent), tetra-n-butylammonium bromide (0.1 equivalent) were added to a dry three-necked flask with a magnetic rotor, the nitrogen was replaced three times, acetic acid (25 mL) was added, and the reaction liquid was nitrogen bubbled for 30 minutes, stirred at room temperature for 12 hours, and then reacted at 120°C for 72 hours, cooled to room temperature, and the solvent was removed by vacuum distillation. The obtained crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 1:1-0:1, and the product was obtained as a yellow solid with a yield of about 40%. MS: molecular weight 739.18.

[0128] Example 4: Synthesis of Tetradentate Metal Platinum (II) Complex Pt-104:

[0129]

[0130] (1) Synthesis of intermediate 1-Cz: 2-Br (1.0 equivalent), 3-Bpin (1.2 equivalent), tetrakistriphenylphosphine palladium (3 mol%) and potassium carbonate (2.0 equivalent) were added to a sealed tube with a magnetic rotor, and nitrogen was replaced three times. 1,4-dioxane (6 mL) and water (1 mL) were added under nitrogen protection. The sealed tube was placed in an oil bath at 85°C and stirred for 50 hours. The mixture was cooled to room temperature, washed with water, and extracted with ethyl acetate. The aqueous layer was extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 50:1-7:1, to obtain a white solid with a yield of about 90%. MS: molecular weight 806.43.

[0131] (2) Synthesis of Pt-104: 1-Cz (1.0 equivalent), potassium chloroplatinate (1.05 equivalent), tetrabutylammonium bromide (0.1 equivalent) were added to a dry three-necked flask with a magnetic rotor, the nitrogen was replaced three times, acetic acid (25 mL) was added, and the reaction liquid was nitrogen bubbled for 30 minutes, stirred at room temperature for 12 hours, and then reacted at 120°C for 72 hours, cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 1:1-0:1, and the product was obtained as a yellow solid with a yield of about 30%. MS: molecular weight 999.38.

[0132] Example 5: Synthesis of Tetradentate Metal Platinum (II) Complex Pt-114:

[0133]

[0134] (1) Synthesis of intermediate 2-Cz: 4-Br (1.0 equivalent), 3-Bpin (1.2 equivalent), tetrakistriphenylphosphine palladium (3 mol%) and potassium carbonate (2.0 equivalent) were added to a sealed tube with a magnetic rotor, and nitrogen was replaced three times. 1,4-dioxane (6 mL) and water (1 mL) were added under nitrogen protection. The sealed tube was placed in an oil bath at 85°C and stirred for 41 hours. The mixture was cooled to room temperature, washed with water, and extracted with ethyl acetate. The aqueous layer was extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 50:1-5:1, to obtain a white solid with a yield of about 80%. MS: molecular weight 559.21.

[0135] (3) Synthesis of Pt-114: 2-Cz (1.0 equivalent), potassium chloroplatinate (1.05 equivalent), tetra-n-butylammonium bromide (0.1 equivalent) were added to a dry three-necked flask with a magnetic rotor, the nitrogen was replaced three times, acetic acid (25 mL) was added, and the reaction liquid was nitrogen bubbled for 30 minutes, stirred at room temperature for 12 hours, and then reacted at 120°C for 72 hours, cooled to room temperature, and the solvent was removed by vacuum distillation. The obtained crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 1:1-0:1, and the product was obtained as a yellow solid with a yield of about 20%. MS: molecular weight 752.16.

[0136] Example 6: Synthesis of Tetradentate Metal Platinum (II) Complex Pt-113:

[0137]

[0138] (1) Synthesis of intermediate 3-Cz: 5-Br (1.0 equivalent), 4-Bpin (1.2 equivalent), tetrakistriphenylphosphine palladium (3 mol%) and potassium carbonate (2.0 equivalent) were added to a sealed tube with a magnetic rotor, and nitrogen was replaced three times. 1,4-dioxane (6 mL) and water (1 mL) were added under nitrogen protection. The sealed tube was placed in an oil bath at 85°C and stirred for 41 hours. The mixture was cooled to room temperature, washed with water, and extracted with ethyl acetate. The aqueous layer was extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 50:1-5:1, to obtain a white solid with a yield of about 85%. MS: molecular weight 543.23.

[0139] (3) Synthesis of Pt-113: 3-Cz (1.0 equivalent), potassium chloroplatinate (1.05 equivalent), tetrabutylammonium bromide (0.1 equivalent) were added to a dry three-necked flask with a magnetic rotor, the nitrogen was replaced three times, acetic acid (25 mL) was added, and the reaction liquid was nitrogen bubbled for 30 minutes, stirred at room temperature for 12 hours, and then reacted at 120°C for 72 hours, cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 1:1-0:1, and the product was obtained as a yellow solid with a yield of about 30%. MS: molecular weight 736.18.

[0140] Example 7: Synthesis of Tetradentate Metal Platinum (II) Complex Pt-134:

[0141]

[0142] (1) Synthesis of intermediate 4-OMe: 6-Br (1.0 equivalent), 1-Bpin (1.2 equivalent), tetrakistriphenylphosphine palladium (3 mol%) and potassium carbonate (2.0 equivalent) were added to a sealed tube with a magnetic rotor, and nitrogen was replaced three times. 1,4-dioxane (6 mL) and water (1 mL) were added under nitrogen protection. The sealed tube was placed in an oil bath at 85°C and stirred for 49 hours. The mixture was cooled to room temperature, washed with water, and extracted with ethyl acetate. The aqueous layer was extracted with ethyl acetate three times, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 50:1-7:1, to obtain a white solid with a yield of about 75%. MS: molecular weight 692.35.

[0143] (2) Synthesis of ligand 4-OH: 4-OMe (1.0 equivalent), pyridine hydrochloride (10 equivalents) and 1,3-dimethyl-2-imidazolidinone (3 mL) were added to the reaction tube in sequence. The nitrogen was replaced three times, and the mixture was placed in an oil bath at 180°C for 12 hours, cooled to room temperature, quenched with sodium bicarbonate solution, extracted three times with ethyl acetate, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 50:1-5:1, to obtain a white solid with a yield of about 80%. MS: molecular weight 678.34.

[0144] (3) Synthesis of Pt-134: 4-OH (1.0 equivalent), potassium chloroplatinate (1.05 equivalent), tetrabutylammonium bromide (0.1 equivalent) were added to a dry three-necked flask with a magnetic rotor, the nitrogen was replaced three times, acetic acid (20 mL) was added, and the reaction liquid was nitrogen bubbled for 30 minutes, stirred at room temperature for 12 hours, and then reacted at 120°C for 72 hours, cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 1:1-0:1, and the product was obtained as a yellow solid with a yield of about 20%. MS: molecular weight 871.29. Photophysical test and theoretical calculation description:

[0145] Steady-state emission experiments and lifetime measurements were performed on a Horiba Jobin Yvon FluoroLog-3 spectrometer. The Pt(II) complex was theoretically calculated using the Titan software package, and the geometry of the ground state (S0) molecule was optimized using density functional theory (DFT). The B3LYP functional was used for DFT calculations, with the 6-31G(d) basis set for C, H, O, S, and N atoms and the LANL2DZ basis set for Pt atoms.

[0146] Experimental data and analysis:

[0147] By the attached Figure 1 It can be seen that Pt-17 can emit strong orange-red light; the quantum efficiency of its polymethyl methacrylate (PMMA) film is greater than 80%, and it can be reused as an OLED light-emitting layer material.

[0148] Density functional theory (DFT) was used to calculate the following structure;

[0149]

[0150] Table 1. DFT theoretical calculation data

[0151]

[0152]

[0153] According to the density functional theory (DFT) calculation results (Table 1, Appendix Figure 2 , Attachment Figure 3 , Attachment Figure 4 ) It can be seen that Pt-1, Pt-77, Pt-49, Pt-61, Pt-79, Pt-80, Pt-101, Pt-113 and Pt-114 have almost the same LUMO orbital distribution, and the LUMO orbital distribution is mainly concentrated on quinoline, and different electron-donating groups have little effect on their LUMO orbital distribution. However, the energy level distribution will change with the change of the electron-donating part and the condensed ring, thereby achieving the regulation of the luminescent color and quantum efficiency. In general, the density functional theory (DFT) calculation results show that the photophysical properties of the luminescent material can be efficiently regulated by adjusting the electron-donating part and the structure of the condensed ring on the material ligand. The above experimental data and theoretical calculation results fully show that the tetradentate ring metal platinum complex phosphorescent material based on 8-phenylquinoline derivatives developed in the present invention application has the characteristics of easy adjustment of HOMO and LUMO orbital energy levels, short excited state lifetime, and high phosphorescence quantum efficiency, indicating that it has great application prospects in the field of OLED.

[0154] Device Embodiment

[0155] Each layer of the organic light-emitting device of the present invention can be formed by vacuum evaporation, sputtering, ion plating and the like, or wet film forming methods such as spin coating, printing, and the like, and the solvent used is not particularly limited.

[0156] In a preferred embodiment of the present invention, the OLED device of the present invention contains a hole transport layer, and the hole transport material can be preferably selected from known or unknown materials, and is particularly preferably selected from the following structures, but it does not mean that the present invention is limited to the following structures:

[0157]

[0158] 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. The preferred p-type dopant of the present invention is the following structure, but it does not mean that the present invention is limited to the following structure:

[0159]

[0160] In a preferred embodiment of the present invention, the electron transport layer can be selected from at least one of compounds ET-1 to ET-13, but this does not mean that the present invention is limited to the following structure:

[0161]

[0162] The electron transport layer may be formed of an organic material and one or more n-type dopants (eg, LiQ).

[0163] OLED device embodiment:

[0164] The structure of the bottom-emitting OLED device is as follows: on glass containing ITO, the hole injection layer (HIL) is HT-1: P-3 (95: 5 v / v%), with a thickness of 10 nanometers; the hole transport layer (HTL) is HT-1, with a thickness of 90 nanometers; the electron blocking layer (EBL) is HT-10, with a thickness of 10 nanometers, the light-emitting layer (EML) is the main material (RH): the platinum metal complex of the present invention (95: 5 v / v%), with a thickness of 35 nanometers, the electron transport layer (ETL) is ET-13: LiQ (50: 50 v / v%), with a thickness of 35 nanometers, and then the cathode Al is evaporated to 70 nanometers. The main material (RH) can be selected from the following structures:

[0165]

[0166]

[0167] The organic light emitting device was prepared by a standard method known in the art at 10 mA / cm 2 Test voltage, efficiency and life under current conditions.

[0168] The performance test results of the organic light-emitting devices prepared in the examples of the present invention and the comparative examples are shown in Table 2.

[0169] Table 2

[0170]

[0171] As can be seen from Table 2, the device structures in the above embodiments and comparative examples are the same except for the light-emitting layer. Based on the device performance of PtON11Me as a reference, the device containing the divalent platinum metal complex of the present invention has significantly improved current efficiency and lifespan compared to conventional organic light-emitting devices. In summary, the novel divalent platinum metal complex of the present invention has great application value in organic optoelectronic devices.

[0172] It will be appreciated by those skilled in the art that the above embodiments are specific embodiments for implementing the present invention, and in practical applications, various changes may be made to them in form and detail 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.

Claims

1. A metal platinum complex, the structure of which is shown in the general formula (1): in, 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 、Y 14 、Y 15 and Y 16 are each independently CH or N; R 1 , R 2 , R 3 , R 4 and R 5 are each independently monosubstituted, disubstituted, trisubstituted, tetrasubstituted or unsubstituted, and R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from hydrogen, deuterium, aryl, alkyl, heteroaryl or a combination thereof; and two or more adjacent R 1 , R 2 , R 3 , R 4 and R 5 Each independently or selectively connected to form a condensed ring; X is NR a , O or S, R a is hydrogen, deuterium, aryl, alkyl or a combination thereof; Z is O, S or NR b , R b is hydrogen, deuterium, aryl, alkyl or a combination thereof; and R b Can be connected with adjacent R 5 Selectively connect to form a fused ring.

2. The metal platinum complex according to claim 1, characterized in that The metal platinum complex is any one of the following structures:

3. An organic light-emitting device, characterized in that: A light-emitting layer comprising the metal platinum complex according to claim 1 or 2 is provided on a substrate.

4. A device, characterized in that The invention comprises at least one cathode, at least one anode and at least one light-emitting layer, wherein at least one of the light-emitting layers comprises the metal platinum complex according to claim 1 or 2.

5. The device according to claim 4, characterized in that The device is a full-color display, a photovoltaic device, a light-emitting display device or an organic light-emitting diode.

6. The device according to claim 4, characterized in that The device is an organic light emitting diode, and its light emitting layer contains the metal platinum complex according to claim 1 or 2 and a corresponding main material, wherein the mass percentage of the metal platinum complex is 1% to 50%, and there is no restriction on the main material.

7. A display or lighting device, characterized in that: The display or lighting device comprises the device according to any one of claims 4 to 6.

8. Use of the metal platinum complex according to any one of claims 1 to 2 in the preparation of organic photoelectric devices.

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