A chiral heptanuclear coin metal cluster compound, its preparation method, and its application

Abstract

This application discloses a chiral hepta-metal cluster compound, its preparation method, and its applications. The chiral hepta-metal cluster compound has the structure shown in Formula I. The chiral hepta-metal cluster compound is used as a luminescent material in lighting and displays, and as a circularly polarized luminescent material in three-dimensional displays, biosensing, encryption, and anti-counterfeiting applications. The chiral hepta-metal cluster compound provided in this application has high luminous efficiency, uses inexpensive and readily available raw materials, is environmentally friendly, has a simple synthesis method, and yields products with high purity and high yield.

Description

Technical Field

[0001] This application relates to a chiral heptode coin metal cluster compound, its preparation method, and its application, belonging to the technical fields of coin metal cluster compound phosphorescent materials and electroluminescent diode applications. Background Technology

[0002] Circularly polarized light emission (CPL) has extremely broad application prospects in fields such as 3D holographic displays, augmented reality (AR) and virtual reality (VR), optical data storage, bioimaging, and quantum information processing. Traditional circularly polarized light is typically generated using a combination of linear polarizers and quarter-wave plates, but this process results in the loss of at least 50% of photons, leading to significant energy loss. In contrast, circularly polarized light-emitting diodes (CP-OLEDs) made from circularly polarized light-emitting materials can directly generate circularly polarized light, with a simpler fabrication process and higher energy utilization. Currently, CP-OLEDs often use chiral organic materials or chiral lanthanide metal complexes as light-emitting materials. However, the complex synthesis process and limited efficiency of these materials restrict the further development and practical application of CP-OLEDs. Therefore, developing new circularly polarized light-emitting materials with simple synthesis processes and high efficiency is of great significance for realizing the practical application of CP-OLEDs.

[0003] Ligand-protected coin metal clusters, due to their unique organic-inorganic hybrid interface and the interactions between ligands and metals, as well as between metals, exhibit advantages such as high luminescence efficiency and good photothermal stability. Furthermore, the synthesis process of these materials is simple, and the luminescence properties of the metal core can be tuned by modifying the ligand structure to meet the needs of practical applications. Moreover, by introducing chiral ligands or inducing chirality in the metal core, these materials can produce circularly polarized luminescence. Therefore, developing new circularly polarized luminescent materials based on coin metal clusters with simple synthesis processes is an ideal choice. Summary of the Invention

[0004] The purpose of this application is to provide a novel chiral heptoderm metal cluster luminescent material, its preparation method, and its application in electroluminescent diodes and circularly polarized light-emitting diodes.

[0005] According to a first aspect of this application, a chiral heptacoin metal cluster compound is provided, the chiral heptacoin metal cluster compound having the structure shown in Formula I:

[0006]

[0007] In Equation I, the valence state of M is +1;

[0008] M is selected from copper or silver;

[0009] X is selected from ClO4 - PF6 - CF3SO3 - BF4 - SbF6 - CF3CF2CF2CF2SO3 - One of them;

[0010] R is independently selected from one of the following: alkyl group (C1-C20), aryl group (C6-C20), heteroaryl group (C5-C20), substituted alkyl group (C1-C2), substituted aryl group (C6-C20), and substituted heteroaryl group (C5-C20);

[0011] The substituents in the substituted alkyl, substituted aryl, and substituted heteroaryl groups are independently selected from one of the following: C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkoxy, amino, halogen, C1-C20 haloalkyl, C6-C20 aryl, and C5-C20 heteroaryl.

[0012] The heteroatom in the heteroaryl group is N.

[0013] Optionally, R is independently selected from one of C1-C8 alkyl, C6-C12 aryl, C5-C12 heteroaryl, C1-C8 substituted alkyl, C6-C12 substituted aryl, and C5-C12 substituted heteroaryl.

[0014] The substituents in the substituted alkyl, substituted aryl, and substituted heteroaryl groups are independently selected from one of the following: C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, C1-C12 alkoxy, C1-C12 haloalkyl, C6-C12 aryl, and C5-C12 heteroaryl.

[0015] Optionally, X represents a monovalent anionic group, and X is selected from ClO4. - Or BF4 - .

[0016] Optionally, R represents a substituent, which may be the same or different, and is independently selected from unsubstituted groups or optionally substituted by one or more Rs, namely: C1-C20 alkyl, C3-20 cycloalkyl, C6-C20 aryl, and C5-C20 heteroaryl.

[0017] The Rs are selected from one of C1-C20 alkyl, C3-C20 cycloalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkoxy, amino, halogen, C1-C20 haloalkyl, C6-C20 aryl, and C5-C20 heteroaryl.

[0018] Optionally, each R may be the same or different and is independently selected from one of phenyl, naphthyl, 4-N,N-dimethyl-phenyl, 4-N,N-diphenyl-phenyl, 4-methoxy-phenyl, 4-ethoxy-phenyl, 4-tert-butyl-phenyl, thienyl, furanyl, dibenzothienyl, dibenzofuranyl, carbazolyl, 4-fluoro-phenyl, 3-fluoro-phenyl, 4-carbazolyl-phenyl, 4-aldehyde-phenyl, 3-aldehyde-phenyl, 2-aldehyde-phenyl, 4-thiomethyl-phenyl, 4-cyano-phenyl, 4-trifluoromethyl-phenyl, and 4-nitro-phenyl.

[0019] Optionally, the chiral heptoderm metal cluster compound belongs to the hexagonal crystal system with space group R3.

[0020] Optionally, the chiral heptametallic metal cluster compound is selected from one of the structures shown in (1) to (8);

[0021]

[0022]

[0023] According to a second aspect of this application, a method for preparing the chiral heptanomeric coin metal cluster compound described above is provided, the method comprising:

[0024] A mixture containing 1,1,1-tris(diphenylphosphine)methane, silveryne compound, binaphthol phosphate, the compound shown in Formula II, and a solvent was reacted to obtain the chiral heptanuclear coin metal cluster compound.

[0025] The binaphthol phosphate is selected from R-binaphthol phosphate or S-binaphthol phosphate;

[0026] The silveryne compound has the structure shown in Formula III;

[0027] M(MeCN)4(X) Equation II;

[0028] RC≡C-Ag Formula III;

[0029] In Formula II, M and X are the same as those described above;

[0030] In Equation III, R is the same as the R mentioned above.

[0031] Optionally, the molar ratio of 1,1,1-tris(diphenylphosphino)methane, silveryne compound, naphthol phosphate, and the compound shown in Formula II is 2:4:3:1 to 2:10:3:1.

[0032] Optionally, the molar volume ratio of 1,1,1-tris(diphenylphosphine)methane to the solvent is 0.1 mmol:(10-20) mL.

[0033] Optionally, the molar volume ratio of the 1,1,1-tris(diphenylphosphine)methane to the solvent is independently selected from any value among 0.1 mmol:10 mL, 0.1 mmol:12 mL, 0.1 mmol:15 mL, 0.1 mmol:18 mL, 0.1 mmol:20 mL, or a range between any two of the above.

[0034] Optionally, the molar volume ratio of 1,1,1-tris(diphenylphosphine)methane to the solvent is 0.1 mmol:(10-15) mL.

[0035] Optionally, the solvent is selected from at least one of dichloromethane, trichloromethane, chlorobenzene, 1,2-dichloroethane, 1,3-dichloropropane, and acetonitrile.

[0036] Optionally, the reaction temperature is 20–60°C, and the reaction time is 4–24 h.

[0037] According to a third aspect of this application, a diode is provided, the diode including a light-emitting layer;

[0038] The light-emitting layer is selected from the chiral heptanuclear coin metal cluster compound described above;

[0039] The diode includes one of organic light-emitting diodes and circularly polarized organic light-emitting diodes.

[0040] Optionally, the weight of the chiral heptoderm metal cluster compound accounts for 1 to 100% of the total weight of the diode light-emitting layer.

[0041] Optionally, the weight of the chiral heptoderm metal cluster compound as a percentage of the total weight of the diode light-emitting layer is independently selected from any value of 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, or a range between any two of the above.

[0042] Optionally, the weight of the chiral heptoderm metal cluster compound accounts for 5-60% of the total weight of the diode light-emitting layer.

[0043] Optionally, the weight of the chiral heptoderm metal cluster compound accounts for 40% of the total weight of the diode light-emitting layer.

[0044] According to a fourth aspect of this application, a method for fabricating the diode described above is provided, the method comprising the following steps:

[0045] S1: A hole transport layer and a hole injection layer are sequentially prepared on a substrate using a solution spin coating method to obtain a substrate containing a hole injection layer;

[0046] S2: A light-emitting layer is prepared on a substrate containing a hole injection layer by solution spin coating to obtain a substrate containing a light-emitting layer;

[0047] S3: On a substrate containing a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode material are sequentially prepared using a vacuum thermal evaporation method to obtain the diode;

[0048] The vacuum degree of the vacuum thermal evaporation method is 4×10⁻⁶. -4 ~4×10 -5 Pa.

[0049] Optionally, the structure of the organic light-emitting diode and the circularly polarized organic light-emitting diode preferably includes the following functional layers: a glass substrate, an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode layer.

[0050] Optionally, the hole injection layer, hole transport layer, and light-emitting layer in the organic light-emitting diode and the circularly polarized organic light-emitting diode are prepared by solution spin coating.

[0051] Optionally, the anode is indium tin oxide (ITO).

[0052] Optionally, the hole injection layer is poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT: PSS), and the hole transport material is poly(bis(4-phenyl)(4-butylphenyl)amine) (Poly-TPD).

[0053] Optionally, the material with hole transport properties is selected from at least one of mCP (1,3-bis(9-carbazole)benzene), 2,6-DCZPPY (2,6-bis(3-(9-carbazole)phenyl)pyridine), TAPC (4,4′-cyclohexylbis(N,N-bis(4-methylphenyl)aniline)), and TCTA (tris(4-(9-carbazole)phenyl)amine).

[0054] Optionally, the material with electron transport properties is selected from at least one of OXD-7 (1,3-bis(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol-2-yl)benzene), BmPyPb (3,3”,5,5”-tetra(3-pyridyl)-1,1':3',1”-terphenyl), TmPyPb (1,3,5-tris((3-pyridyl)-3-phenyl)benzene), TPBi (1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene), and BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline).

[0055] Optionally, the light-emitting layer contains a chiral heptenoid metal cluster compound of Formula I and a host material, wherein the host material is selected from at least one of TCTA, mCP, 2,6-DCZPPY, OXD-7, BCP, and TPBi, and more preferably 2,6-DCZPPY and OXD-7 (in a mass percentage of 1:1).

[0056] Optionally, the electron injection layer material is LiF.

[0057] Optionally, the cathode material is metallic Al.

[0058] Optionally, the preferred diode structure is: ITO / PEDOT: PSS (50nm) / Poly-TPD (30nm) / 30wt% 2,6-DCZPPY: 30wt% OXD-7: 40wt% Chiral heptode metal cluster compound (50nm) shown in Formula I / BmPyPb (50nm) / LiF (1nm) / Al (100nm).

[0059] According to the fifth aspect of this application, an application of the aforementioned diode in the fields of flat panel display, daily lighting, three-dimensional display, biosensing, and encryption anti-counterfeiting is provided.

[0060] Optionally, the organic light-emitting diodes and circularly polarized organic light-emitting diodes can be used in flat panel displays and everyday lighting, and their circularly polarized light emission can be further applied to three-dimensional displays, biosensing, encryption and anti-counterfeiting, and other fields.

[0061] As an optional implementation, this application is achieved through the following technical solution:

[0062] The specific reaction equation is as follows:

[0063]

[0064] (1) The ligand 1,1,1-tris(diphenylphosphine)methane and the silveryne compound (RC≡C-Ag) were poured into dichloromethane solvent and stirred.

[0065] (2) Then, add the naphthol phosphate and M(MeCN)4(X) into the solution of step (1) and stir for 4 hours to prepare a chiral heptanuclear metal cluster compound.

[0066] Optionally, M(MeCN)4(X) refers to Ag(MeCN)4(X) or Cu(MeCN)4(X).

[0067] Optionally, the method for fabricating the organic light-emitting diode and the circularly polarized organic light-emitting diode includes: (1) preparing the hole injection layer and the hole transport layer in the organic light-emitting diode and the circularly polarized organic light-emitting diode using a solution spin coating method; (2) preparing a light-emitting layer containing the chiral heptenoid metal cluster compound shown in doped formula I using a solution spin coating method; (3) performing vacuum thermal evaporation (vacuum degree less than 4×10⁻⁶) on the organic light-emitting diode and the circularly polarized organic light-emitting diode. -4 The electron transport layer material, electron injection layer material, and cathode material of the device are deposited sequentially by the method of Pa).

[0068] In this application, the term "C1-C20 alkyl" should be understood to preferably refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably C1-C20 alkyl. "C1-C10 alkyl" should be understood to preferably refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, or isomers thereof. In particular, the group has 1, 2, 3, 4, 5 or 6 carbon atoms (“C1 to C6 alkyl”), such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and more particularly, the group has 1, 2 or 3 carbon atoms (“C1 to C3 alkyl”), such as methyl, ethyl, n-propyl or isopropyl.

[0069] In this application, the term "C2-C20 alkenyl" should be understood to refer to a straight-chain or branched monovalent hydrocarbon group containing one or more double bonds and having 2 to 20 carbon atoms, preferably "C2-C10 alkenyl". "C2-C10 alkenyl" should be understood to preferably refer to a straight-chain or branched monovalent hydrocarbon group containing one or more double bonds and having 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms, particularly 2 or 3 carbon atoms ("C2-C3 alkenyl"). It should be understood that when the alkenyl group contains more than one double bond, the double bonds may be separable or conjugated. The alkenyl group is, for example, vinyl, allyl, (E)-2-methylvinyl, (Z)-2-methylvinyl, (E)-but-2-enyl, (Z)-but-2-enyl, (E)-but-1-enyl, (Z)-but-1-enyl, pent-4-enyl, (E)-pent-3-enyl, (Z)-pent-3-enyl, (E)-pent-2-enyl, (Z)-pent-2-enyl, (E)- Pentyl-1-enyl, (Z)-pentyl-1-enyl, hex-5-enyl, (E)-hex-4-enyl, (Z)-hex-4-enyl, (E)-hex-3-enyl, (Z)-hex-3-enyl, (E)-hex-2-enyl, (Z)-hex-2-enyl, (E)-hex-1-enyl, (Z)-hex-1-enyl, isopropenyl, 2-methylprop-2-enyl, 1-methylprop-2-enyl 2-Methylprop-1-enyl, (E)-1-methylprop-1-enyl, (Z)-1-methylprop-1-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, (E)-2-methylbut-2-enyl, (Z)-2-methylbut-2-enyl, (E)-1-methylbut-2-enyl, (Z)-1-methyl But-2-enyl, (E)-3-methylbut-1-enyl, (Z)-3-methylbut-1-enyl, (E)-2-methylbut-1-enyl, (Z)-2-methylbut-1-enyl, (E)-1-methylbut-1-enyl, (Z)-1-methylbut-1-enyl, 1,1-dimethylprop-2-enyl, 1-ethylprop-1-enyl, 1-propylvinyl, 1-isopropylvinyl.

[0070] In this application, the term "C2-C20 ynyl" should be understood to refer to a straight or branched monovalent hydrocarbon group containing one or more triple bonds and having 2 to 20 carbon atoms, preferably "C2-C10 ynyl". The term "C2-C10 ynyl" should also be understood to preferably refer to a straight or branched monovalent hydrocarbon group containing one or more triple bonds and having 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms, particularly 2 or 3 carbon atoms ("C2-C3 ynyl"). The alkyne group is, for example, ethynyl, prop-1-ynyl, prop-2-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, pent-1-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, hex-1-ynyl, hex-2-ynyl, hex-3-ynyl, hex-4-ynyl, hex-5-ynyl, 1-methylprop-2-ynyl, 2-methylbut-3-ynyl, 1-methylbut-3-ynyl, 1-methylbut-2-ynyl, 3-methylbut-1-ynyl, 1-ethylprop-2-ynyl, 3-methylpent-4-ynyl, 2-methylpent-4-ynyl -Alynyl, 1-methylpentan-4-ynyl, 2-methylpentan-3-ynyl, 1-methylpentan-3-ynyl, 4-methylpentan-2-ynyl, 1-methylpentan-2-ynyl, 4-methylpentan-1-ynyl, 3-methylpentan-1-ynyl, 2-ethylbutan-3-ynyl, 1-ethylbutan-3-ynyl, 1-ethylbutan-2-ynyl, 1-propylpropan-2-ynyl, 1-isopropylpropan-2-ynyl, 2,2-dimethylbutan-3-ynyl, 1,1-dimethylbutan-3-ynyl, 1,1-dimethylbutan-2-ynyl, or 3,3-dimethylbutan-1-ynyl. In particular, the ynyl group is ethynyl, propan-1-ynyl, or propan-2-ynyl.

[0071] In this application, the term "C3-C20 cycloalkyl" should be understood as referring to a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3 to 20 carbon atoms, preferably "C3-C10 cycloalkyl". The term "C3-C10 cycloalkyl" should also be understood as referring to a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. The C3-C10 cycloalkyl group can be a monocyclic hydrocarbon group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl, or a bicyclic hydrocarbon group, such as decahydronaphthalene ring.

[0072] In this application, the term "C6-C20 aryl" should be understood to mean a monocyclic, bicyclic, or tricyclic hydrocarbon ring having 6 to 20 carbon atoms with monovalent aromaticity or partial aromaticity, preferably "C6-C14 aryl". The term "C6-C14 aryl" should be understood to preferably refer to a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C6-C14 aryl") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms, particularly a ring having 6 carbon atoms ("C6 aryl"), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C9 aryl"), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C10 aryl"), such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or a ring having 13 carbon atoms ("C13 aryl"), such as fluorenyl, or a ring having 14 carbon atoms ("C14 aryl"), such as anthracene.

[0073] The term "C5-C20 heteroaryl" should be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O, and S, such as "C5-C14 heteroaryl". The term "C5-C14 heteroaryl" should also be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 ring atoms, particularly 5, 6, 9, or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3, heteroatoms independently selected from N, O, and S, and in each case, may be benzofused. Specifically, the heteroaryl group is selected from thiophene, furanyl, pyrroleyl, oxazolyl, thiazolyl, imidazoleyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiazolyl, and thiazolyl. -4H-pyrazolyl and their benzo[derivatives], such as benzofuranyl, benzothiophenyl, benzooxazolyl, benzoisooxazolyl, benzoimidazolyl, benzotriazolyl, indazole, indolyl, isoindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, etc., and their benzo[derivatives], such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or acrylinyl, inazinyl, purinyl, etc., and their benzo[derivatives]; or cyclolinyl, phthalazinyl, quinazolinyl, quinoxolinyl, naphridinyl, pteridinyl, carbazolyl, acridineyl, phenazinyl, phenothiazinyl, phenothiazinyl, etc.

[0074] Unless otherwise stated, heterocyclic, heteroaryl, or heteroaryl groups include all their possible isomers, such as their positional isomers. Thus, for some illustrative, non-limiting examples, pyridyl or pyridylene includes pyridin-2-yl, pyridin-2-yl, pyridin-3-yl, pyridin-3-yl, pyridin-4-yl, and pyridin-4-yl; thiophenyl or thiophene includes thiophene-2-yl, thiophene-2-yl, thiophene-3-yl, and thiophene-3-yl.

[0075] The above definition of the term "C1-C20 alkyl" also applies to other terms containing "C1-C20 alkyl", such as the terms "C1-C2 alkoxy" and "C1-C20 haloalkyl".

[0076] The beneficial effects that this application can produce include:

[0077] The chiral heptanuclear metal clusters provided in this application possess advantages such as high luminescence efficiency, low toxicity, easy synthesis, low cost, and tunable emission color. These chiral heptanuclear metal clusters are ionic and readily soluble in common organic solvents, making them particularly suitable for solution-based fabrication of electroluminescent devices, thus reducing device fabrication costs. These clusters exhibit strong luminescence in both solution and thin-film states. They can be used as guest materials to dope host materials for the fabrication of organic light-emitting diodes (OLEDs). The binatol phosphate ligand used in the chiral heptanuclear coin metal clusters is chiral (R-binatol phosphate / S-binatol phosphate), which can induce chirality in the heptanuclear coin metal clusters, further enabling circularly polarized luminescence. Therefore, these chiral heptanuclear coin metal clusters can be used as chiral luminescent materials to fabricate circularly polarized OLEDs. Attached Figure Description

[0078] Figure 1 Figure 1 shows the crystal structure diagrams of cluster compounds (1) and (2) in Examples 1 and 2 of this application. Figure 2a is the X-ray single crystal diffraction structure diagram of cluster compound (1) in Example 1, and Figure 2b is the X-ray single crystal diffraction structure diagram of cluster compound (2) in Example 2.

[0079] Figure 2 The following are the emission spectra of the solutions and solids of cluster compounds (1) and (2) in Examples 1 and 2 of this application under 365 nm excitation. Figure a shows the emission spectra of cluster compounds (1) and (2) in dichloromethane solution, and Figure b shows the emission spectra of cluster compounds (1) and (2) in solid powder.

[0080] Figure 3 The following are the circularly polarized emission spectra of the solutions and solids of cluster compounds (1) and (2) in Examples 1 and 2 of this application under 365 nm excitation: Figure a is the photo-induced circularly polarized emission spectrum of cluster compounds (1) and (2) in dichloromethane solution; Figure b is the asymmetry factor diagram of the photo-induced circularly polarized emission of cluster compounds (1) and (2) in dichloromethane solution; Figure c is the photo-induced circularly polarized emission spectrum of cluster compounds (1) and (2) in solid powder; and Figure d is the asymmetry factor diagram of the photo-induced circularly polarized emission of cluster compounds (1) and (2) in solid powder.

[0081] Figure 4The circularly polarized emission spectra generated by the circularly polarized electroluminescent devices of cluster compounds (1) and (2) in Examples 1 and 2 of this application are shown in Figure a. The electro-circularly polarized emission spectra of cluster compounds (1) and (2) in a circularly polarized light-emitting diode are shown in Figure b. The asymmetry factor of electro-circularly polarized emission of cluster compounds (1) and (2) in a circularly polarized light-emitting diode are shown in Figure b. Detailed Implementation

[0082] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0083] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0084] The crystal structures of the chiral heptanuclear coin metal clusters (1)-(2) prepared in the following examples were determined by single-crystal X-ray diffraction, and their unit cell parameters are shown in Table 1. Their structures were further confirmed by high-resolution electrospray ionization mass spectrometry (HR-ESI-MS). The purity of the obtained clusters (1)-(2) was determined by proton NMR spectroscopy, phosphorus NMR spectroscopy, and elemental analysis (C, H, and N).

[0085] In this application, the chiral heptametallic metal cluster compounds are selected from the cluster compounds (1) to (8) shown below, where Ph represents phenyl in the structural formula of cluster compounds (1) to (8):

[0086]

[0087]

[0088] According to an embodiment of the present invention, the chiral heptanuclear metal clusters (1) to (6) have the unit cell parameters shown in Table 1 below:

[0089] Table 1: Cell parameters of chiral heptodecoin metal clusters (1) to (6)

[0090]

[0091]

[0092] Example 1 Preparation of cluster compound (1)

[0093] Weigh 0.1 mmol (28.5 mg) of 1,1,1-tris(diphenylphosphino)methane and 0.3 mmol (56.5 mg) of 4-(diphenylamino)phenyl)ethynylsilver, and add 15 mL of dichloromethane. After stirring at room temperature for 15 minutes, add 0.15 mmol (52.3 mg) of R-binaphthol phosphate and 0.05 mmol (16.4 mg) of Cu(CH3CN)4ClO4, and then react at room temperature in the dark for 4 hours. After the reaction is complete, filter the reaction solution and remove the solvent using a rotary evaporator. Wash three times with diethyl ether (3 × 10 mL) to obtain a red powder with a yield of 85.2% (based on Cu(CH3CN)4ClO4). 1H and 1P NMR spectroscopy showed that the product was pure (100% purity). Figure 1 As shown, Figure 1 Figure a shows the X-ray single-crystal diffraction structure of cluster compound (1) in Example 1. As can be seen from Figure a, cluster compound (1) is a 7-nucleated heterometallic cluster compound composed of 6 silver atoms and 1 copper atom. The metal core is surrounded by a ligand protective layer composed of 2 1,1,1-tris(diphenylphosphine)methane, 3 4-(diphenylamino)phenylacetylene, and 3 R-binaphthol phosphates.

[0094] High-resolution mass spectrometry: [M-ClO4] +

[0095] Calculated value: 3694.1722

[0096] Test value: 3694.1627

[0097] Elemental analysis:

[0098] Calculated values: C: 61.41%; H: 3.72%; N: 1.11%;

[0099] Test values: C: 61.54%; H: 3.73%; N: 1.11%.

[0100] 1 H NMR(400MHz,Methylene Chloride-d2)δ8.55(d,J=8.8Hz,6H),7.91(dd,J=8.4,4.4Hz,19H),7.63(s,13H),7.43-7.35( m,13H),7.34-7.14(m,23H),7.13-6.94(m,46H),6.90(t,J=7.3Hz,7H),6.51(t,J=7.5Hz,12H).

[0101] 31P NMR (162MHz, Methylene Chloride-d2) δ13.15 (d, J = 567Hz, 6P), 11.45, 9.04 (3P).

[0102] Example 2 Preparation of cluster compound (2)

[0103] Weigh 0.1 mmol (28.5 mg) of 1,1,1-tris(diphenylphosphino)methane and 0.3 mmol (56.5 mg) of 4-(diphenylamino)phenyl)ethynyl silver, and add 15 mL of dichloromethane. After stirring at room temperature for 15 minutes, add 0.15 mmol (52.3 mg) of S-binaphthol phosphate and 0.05 mmol (16.4 mg) of Cu(CH3CN)4ClO4, and then react at room temperature in the dark for 4 hours. After the reaction is complete, filter the reaction solution and remove the solvent using a rotary evaporator. Wash three times with diethyl ether (3 × 10 mL) to obtain a red powder with a yield of 86.2% (based on Cu(CH3CN)4ClO4). 1H and 1P NMR spectroscopy showed that the product was pure (100% purity). Figure 1 As shown, Figure 1 Figure b shows the X-ray single-crystal diffraction structure of cluster (2) in Example 2. As can be seen from Figure b, cluster (2) is a 7-nucleated heterometallic cluster composed of 6 silver atoms and 1 copper atom. The metal core is surrounded by a ligand protective layer composed of 2 1,1,1-tris(diphenylphosphine)methane, 3 4-(diphenylamino)phenylacetylene, and 3 S-binaphthol phosphate.

[0104] High-resolution mass spectrometry: [M-ClO4] +

[0105] Calculated value: 3694.1722

[0106] Test value: 3694.1627

[0107] Elemental analysis:

[0108] Calculated values: C: 61.41%; H: 3.72%; N: 1.11%;

[0109] Test values: C: 61.74%; H: 3.74%; N: 1.11%.

[0110] 1H NMR(400MHz,Methylene Chloride-d2)δ8.59-8.49(m,6H),7.94-7.83(m,18H),7.62(s,12H),7.45-7.34(m,13H),7 .35-7.14(m,22H),7.15-6.95(m,46H),6.90(td,J=7.1,1.3Hz,8H),6.51(t,J=7.2Hz,12H).

[0111] 31 P NMR (162MHz, Methylene Chloride-d2) δ13.15 (d, J = 567Hz, 6P), 11.45, 8.96 (3P).

[0112] Example 3 Photoluminescence performance test of clusters (1) and (2)

[0113] The excitation spectrum, emission spectrum, luminescence lifetime, and luminescence quantum yield of the cluster compounds (1) and (2) prepared in Examples 1-2 were measured using an Edinburgh FLS1000 fluorescence spectrometer in dichloromethane solution and solid powder states, respectively. The luminescence quantum yield of the samples was determined using an integrating sphere with a diameter of 142 mm. The specific results are shown in Table 2.

[0114] Table 2. Photoluminescence properties of chiral heptametallic metal clusters (1) and (2) in dichloromethane solution and solid powder states.

[0115]

[0116] Table 2 shows that both clusters (1) and (2) exhibit red light emission in dichloromethane solution and solid form, with the maximum emission peak around 620 nm. The quantum yields of luminescence for clusters (1) and (2) in dichloromethane solution reach 91.8% and 90.3%, respectively. As excellent luminescent materials, they can be used to prepare organic light-emitting diodes (OLEDs) and further applied in lighting, flat panel displays, and other fields. The emission spectra of clusters (1) and (2) in dichloromethane solution and solid powder form under photoexcitation are shown in the appendix. Figure 2 , Figure 2Cluster 1 corresponds to cluster (1), and cluster 2 corresponds to cluster (2). Figure a shows the emission spectra of clusters (1) and (2) in dichloromethane solution. The figure shows that both clusters exhibit bright red emission in dichloromethane solution, with their emission centers located at 666 nm and 667 nm, respectively. Figure b shows the emission spectra of clusters (1) and (2) in solid powder form. Compared with the emission spectra in dichloromethane solution, the emission of these two clusters in solid powder shows a red shift, with their emission centers shifting to 680 nm and 683 nm, respectively.

[0117] Example 4: Circularly polarized luminescence performance test of clusters (1) and (2)

[0118] The circular polarization luminescence properties of the cluster compounds (1) and (2) prepared in Examples 1-2 were tested in dichloromethane solution and solid states using a CPL-300 circular polarization luminescence spectrometer, including the circular polarization luminescence spectra and luminescence asymmetry factors. The specific results are shown in Table 3.

[0119] Table 3. Circular polarization luminescence properties of chiral heptametallic clusters (1) and (2) in dichloromethane solution and solid powder states.

[0120]

[0121] As shown in Table 3, under photoexcitation, both cluster compounds (1) and (2) exhibit circularly polarized luminescence properties in both dichloromethane solution and solid powder states. Cluster compound (1) shows a negative circularly polarized luminescence signal in both solution and solid states, while cluster compound (2) shows a positive circularly polarized luminescence signal in both solution and solid powder states. The luminescence asymmetry factors of both in the solid powder state can reach -5.4 × 10⁻⁶. -3 and 5.2×10 -3 As shown in Table 3, clusters 1 and 2 exhibit excellent circularly polarized luminescence properties and can be used as circularly polarized luminescent materials to prepare circularly polarized electroluminescent diodes, which can be applied in fields such as three-dimensional displays, biosensing, and encryption / anti-counterfeiting. The circularly polarized luminescence spectra of clusters (1) and (2) are shown in the appendix. Figure 3 , Figure 3 Cluster 1 corresponds to cluster (1), and cluster 2 corresponds to cluster (2); from Figure 3As can be seen from the figures, Figure a shows the photo-induced circularly polarized emission spectra of clusters (1) and (2) in dichloromethane solution; Figure b shows the asymmetry factor of photo-induced circularly polarized emission of clusters (1) and (2) in dichloromethane solution; Figure c shows the photo-induced circularly polarized emission spectra of clusters (1) and (2) in solid powder; and Figure d shows the asymmetry factor of photo-induced circularly polarized emission of clusters (1) and (2) in solid powder. Figures a and c show that clusters (1) and (2) exhibit mirror-symmetric photo-induced circularly polarized emission spectra in both dichloromethane solution and solid powder. Figures b and d show that clusters (1) and (2) have larger asymmetry factors in solid powder, with values ​​of -5.4 × 10⁻⁶. -3 and 5.2×10 -3 .

[0122] Example 5: Using cluster compound (1) as a luminescent material, organic light-emitting diodes were prepared by solution method.

[0123] Using the cluster compound (1) prepared in Example 1 as the luminescent material, an organic light-emitting diode was prepared by doping it with 40% by weight into a mixed host material of OXD-7 (30%): 2,6-DCZPPY (30%) as the luminescent layer. The device structure was: ITO / PEDOT:PSS (20nm) / Poly-TPD (30nm) / 30% OXD-7:% 2,6-DCZPPY:40wt% cluster compound 1 (50nm) / BmPyPb (50nm) / LiF (1nm) / Al (100nm).

[0124] The ITO glass was cleaned with glass cleaner, then ultrasonically cleaned sequentially with pure water, acetone, and isopropanol for 15 minutes each, and finally treated with ultraviolet ozone for 40 minutes. First, saturated poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT:PSS) was filtered and spin-coated onto the ITO glass at 3600 rpm. It was then placed in a forced-air drying oven and dried at 130°C for 20 minutes to obtain a 40 nm thick hole transport layer. Next, the ITO glass coated with the hole transport layer was transferred to a glove box, and a filtered poly(bis(4-phenyl)(4-butylphenyl)amine) (Poly-TPD) chlorobenzene solution (20 mg / ml) was spin-coated onto the PEDOT:PSS film. Annealing at 140°C for 20 minutes formed a 10 nm thick hole injection layer. After cooling to 25°C, a dichloromethane solution (concentration 5 mg / ml) containing 1,3-bis(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol-2-yl)benzene (OXD-7) (30%): 2,6-DCZPPY (30%): 40 wt% cluster 1 (weight percentage) was spin-coated onto a Poly-TPD film at 2400 rpm to form a 50 nm thick luminescent layer. The luminescent layer was dried at 40°C for 25 minutes. Finally, the ITO substrate was placed in the evaporation chamber, and the vacuum degree was lower than 4 × 10⁻⁶. -4 At Pa, a 50 nm thick BmPyPb electron transport layer, a 1 nm thick LiF electron injection layer, and a 100 nm thick Al electrode are sequentially thermally deposited as the device cathode. A mask is required when depositing the Al electrode. The emitting area of ​​the organic light-emitting diode device based on the cluster compound (1) is 16 mm². 2 .

[0125] The performance of the light-emitting diode (LED) device was tested in a dry, room-temperature air environment. Electroluminescence performance parameters included the turn-on voltage (V). on Brightness is 1 cd / m 2 (voltage), maximum brightness (L) max Maximum current efficiency (CE) max Maximum power efficiency (PE) max Maximum external quantum efficiency (EQE) max ) and electroluminescence wavelength (λ) EL These data are listed in Table 4.

[0126] Table 4. Performance data of cluster compound 1 as a luminescent material in the preparation of organic light-emitting diodes.

[0127]

[0128] As shown in Table 4, the organic light-emitting diodes prepared by solution method using cluster compound 1 as the light-emitting material exhibit excellent performance, with a maximum external quantum efficiency (EQE) of 26.7%.

[0129] Example 6: Using clusters (1) and (2) as luminescent materials, circularly polarized organic light-emitting diodes were prepared by solution method.

[0130] Using the method in Example 5, organic light-emitting diodes were first prepared by using clusters (1) and (2) as luminescent materials and by solution method, and then their circularly polarized electroluminescence spectra were tested by using a CPL-300 circularly polarized emission spectrometer.

[0131] Using clusters (1) and (2) as luminescent materials, respectively, circularly polarized organic light-emitting diodes (OLEDs) prepared by solution method exhibited excellent electro-polarized luminescence performance, with circularly polarized electroluminescence wavelengths of 675 nm and 677 nm, respectively; and circularly polarized electroluminescence asymmetry factors of -0.6 × 10⁻⁶, respectively. -4 and 0.6×10 -4 The electro-circularly polarized emission spectrum of the clusters is shown in the appendix. Figure 4 , Figure 4 Cluster 1 corresponds to cluster (1), and cluster 2 corresponds to cluster (2); from Figure 4 As can be seen from Figure a, a is the electro-circularly polarized emission spectrum of clusters (1) and (2) in a circularly polarized light-emitting diode, and b is the electro-circularly polarized emission asymmetry factor diagram of clusters (1) and (2) in a circularly polarized light-emitting diode. Figure a shows that clusters (1) and (2) exhibit mirror-symmetric electro-circularly polarized emission spectra, with electro-circularly polarized emission asymmetry factors of -5.2 × 10⁻⁶ and -10⁻⁶, respectively. -3 and 5.3×10 -3 (See Figure b).

[0132] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A chiral heptanuclear coin metal cluster compound, characterized in that, The chiral heptametallic cluster compound has the structure shown in Formula I: Formula I; In Equation I, the valence state of M is +1; M is selected from copper or silver; X is selected from ClO4 - PF6 - CF3SO3 - BF4 - SbF6 - CF3CF2CF2CF2SO3 - One of them; R is independently selected from one of the following: alkyl group (C1-C20), aryl group (C6-C20), heteroaryl group (C5-C20), substituted alkyl group (C1-C8), substituted aryl group (C6-C20), and substituted heteroaryl group (C5-C20); The substituents in the substituted alkyl, substituted aryl, and substituted heteroaryl groups are independently selected from one of the following: C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkoxy, halogen, C1-C20 haloalkyl, C6-C20 aryl, and C5-C20 heteroaryl. The heteroatom in the heteroaryl group is N.

2. The chiral heptanuclear coin metal cluster compound according to claim 1, characterized in that, The R is independently selected from one of the following: C1-C8 alkyl, C6-C12 aryl, C5-C12 heteroaryl, C1-C8 substituted alkyl, C6-C12 substituted aryl, and C5-C12 substituted heteroaryl; The substituents in the substituted alkyl, substituted aryl, and substituted heteroaryl groups are independently selected from one of the following: C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, C1-C12 alkoxy, C1-C12 haloalkyl, C6-C12 aryl, and C5-C12 heteroaryl. The chiral heptametallic cluster compound belongs to the hexagonal crystal system, space group [space group missing]. R 3.

3. A chiral heptanuclear coin metal cluster compound, characterized in that, The chiral heptametallic metal cluster compound is selected from one of the structures shown in (1) to (8); 。 4. The method for preparing the chiral heptanomeric coin metal cluster compound according to claim 1, characterized in that, The preparation method includes: A mixture containing 1,1,1-tris(diphenylphosphine)methane, silveryne compound, binaphthol phosphate, the compound shown in Formula II, and a solvent was reacted to obtain the chiral heptanuclear coin metal cluster compound. The binaphthol phosphate is selected from R-binaphthol phosphate or S-binaphthol phosphate; The silveryne compound has the structure shown in Formula III; M(MeCN)4(X) Equation II; RC≡C-Ag type III; In Formula II, M and X are the same as M and X in claim 1; In Formula III, R is the same as R in claim 1.

5. The preparation method according to claim 4, characterized in that, The molar ratio of 1,1,1-tris(diphenylphosphino)methane, silveryne compound, binaphthol phosphate, and the compound shown in Formula II is 2:4:3:1 to 2:10:3:1; The molar volume ratio of the 1,1,1-tris(diphenylphosphino)methane to the solvent is 0.1 mmol: (10~20) mL.

6. The preparation method according to claim 4, characterized in that, The molar volume ratio of the 1,1,1-tris(diphenylphosphino)methane to the solvent is 0.1 mmol: (10~15) mL.

7. The preparation method according to claim 4, characterized in that, The solvent is selected from at least one of dichloromethane, trichloromethane, chlorobenzene, 1,2-dichloroethane, 1,3-dichloropropane, and acetonitrile; The reaction temperature is 20~60℃, and the reaction time is 4~24h.

8. A diode, characterized in that, The diode includes a light-emitting layer; The light-emitting layer is selected from the chiral heptanuclear coin metal cluster compound according to any one of claims 1 to 3; The diode includes one of organic light-emitting diodes and circularly polarized organic light-emitting diodes.

9. The diode according to claim 8, characterized in that, The weight of the chiral heptoderm metal cluster compound accounts for 1 to 100% of the total weight of the diode light-emitting layer.

10. The diode according to claim 8, characterized in that, The weight of the chiral heptametallic cluster compound accounts for 5-60% of the total weight of the diode light-emitting layer.

11. A method for fabricating a diode according to any one of claims 8 to 10, characterized in that, The preparation method includes the following steps: S1: A hole transport layer and a hole injection layer are sequentially prepared on a substrate using a solution spin coating method to obtain a substrate containing a hole injection layer; S2: A light-emitting layer is prepared on a substrate containing a hole injection layer by solution spin coating to obtain a substrate containing a light-emitting layer; S3: On a substrate containing a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode material are sequentially prepared by vacuum thermal evaporation to obtain the diode; The vacuum degree of the vacuum thermal evaporation method is 4×10⁻⁶. -4 ~4×10 -5 Pa.

12. The application of the diode according to any one of claims 8 to 10 in the fields of flat panel display, daily lighting, three-dimensional display, biosensing, and encryption anti-counterfeiting.

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