Cyclometallated bisacetylene platinum (II) complex and its preparation method and application

Abstract

The present invention relates to the field of organic synthesis, and discloses a cyclometallated bisacetylene platinum (II) complex, a preparation method thereof and an application thereof. A cyclometallated bisacetylene platinum (II) complex has a structure as shown in formula (1), wherein R is selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 heteroaryl, substituted or unsubstituted C1-C6 aryl, or -SO3Na; R' is selected from hydrogen, substituted or unsubstituted C1-C6 alkane, substituted or unsubstituted C1-C6 alkene, or substituted or unsubstituted C1-C6 anilino; and the substituents optionally present on R and R' are each independently selected from one or more of C1-C3 alkyl, C1-C3 alkoxy and halogen. The preparation method of the present invention is simple, the reaction conditions are mild, and the yield is high. #imgabs0#

Description

Technical Field

[0001] The invention relates to the field of organic synthesis, and in particular to a cyclometallated bis-acetylene platinum (II) complex and a preparation method and application thereof. Background Art

[0002] Phosphorescent metal complexes have great potential in the fields of solar cells, organic light-emitting diodes and biological applications, which has aroused people's interest in studying the field of phosphorescent metal complexes to continuously excite efficient phosphorescence. In particular, metal platinum (II) complexes have efficient phosphorescence and unique excited state characteristics. For example, platinum (II) complexes supported by bipyridine derivatives and aryl ethynyl ligands show high emission quantum efficiency and short emission lifetime. They are very potential application values ​​in OLED applications as luminescent materials, whether used as dopant materials or for extending service life or color adjustment. The emission energy of these Pt (II) complexes can be adjusted by changing the substituents on the aryl ethynyl group or changing the bipyridine ligand and its derivatives. However, there are few reports on cyclometallated bisacetylene platinum (II) complexes in the prior art. Therefore, it is urgent to develop a method for synthesizing cyclometallated bisacetylene platinum (II) complexes. Summary of the invention

[0003] The purpose of the present invention is to overcome the above problems existing in the prior art and provide a cyclometallated bisacetylene platinum (II) complex and a preparation method and application thereof. The preparation method of the present invention is simple, the reaction conditions are mild and the yield is high.

[0004] In order to achieve the above object, the first aspect of the present invention provides a cyclometallated bisacetylene platinum (II) complex, wherein the platinum (II) complex has a structure as shown in formula (1):

[0005]

[0006] Wherein, R is selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 heteroaryl, substituted or unsubstituted C1-C6 aryl, or -SO3Na; R' is selected from hydrogen, substituted or unsubstituted C1-C6 alkane, substituted or unsubstituted C1-C6 alkene, or substituted or unsubstituted C1-C6 anilino; and the substituents optionally present on R and R' are each independently selected from one or more of C1-C3 alkyl, C1-C3 alkoxy and halogen.

[0007] Preferably, R is a tert-butyl group or a trifluoromethyl group; and R' is a hydrogen atom, a trifluoromethyl group or a diphenylamino group.

[0008] The second aspect of the present invention provides a method for preparing a cyclometallated bisacetylene platinum (II) complex, comprising: contacting a compound represented by formula (2) with a compound represented by formula (3) in an inert atmosphere in the presence of an alkaline substance, a catalyst and a solvent,

[0009]

[0010] Wherein, R is selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 heteroaryl, substituted or unsubstituted C1-C6 aryl, or -SO3Na; R' is selected from hydrogen, substituted or unsubstituted C1-C6 alkane, substituted or unsubstituted C1-C6 alkene, or substituted or unsubstituted C1-C6 anilino; and the substituents optionally present on R and R' are each independently selected from one or more of C1-C3 alkyl, C1-C3 alkoxy and halogen.

[0011] Preferably, R is a tert-butyl group or a trifluoromethyl group; and R' is a hydrogen atom, a trifluoromethyl group or a diphenylamino group.

[0012] Preferably, the compound represented by formula (2) is

[0013] Preferably, the compound represented by formula (3) is

[0014] The third aspect of the present invention provides a cyclometallated bisacetylene platinum (II) complex prepared by the above method.

[0015] The fourth aspect of the present invention provides the use of the above-mentioned cyclometallated bisacetylene platinum (II) complex.

[0016] Through the above technical scheme, the cyclometallated bisacetylene platinum (II) complex shown in formula (1) shows unique emission properties in the solid state, such as color change, mechanical coloring, etc.; in addition, the cyclometallated bisacetylene platinum (II) complex shown in formula (1) has improved stability and solubility under physiological conditions.

[0017] The inventors of the present invention have found through in-depth research that, under the protection of inert gas, in the presence of an organic solvent, in the presence of an alkaline substance, a catalyst and a solvent, the compound represented by formula (2)

[0018] The compound represented by formula (3) The method can not only prepare the cyclometallated bisacetylene platinum (II) complex represented by formula (1), but also complete the preparation of the cyclometallated bisacetylene platinum (II) complex in one step. The preparation method has the advantages of simple process, mild reaction conditions and high yield. DETAILED DESCRIPTION

[0019] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0020] In the present invention, unless otherwise specified, -tBu represents a tert-butyl group, -CF3 represents a trifluoromethyl group, and -NPh2 represents a diphenylamino group.

[0021] The first aspect of the present invention provides a cyclometallated bisacetylene platinum (II) complex, wherein the platinum (II) complex has a structure as shown in formula (1):

[0022]

[0023] Wherein, R is selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 heteroaryl, substituted or unsubstituted C1-C6 aryl, or -SO3Na; R' is selected from hydrogen, substituted or unsubstituted C1-C6 alkane, substituted or unsubstituted C1-C6 alkene, or substituted or unsubstituted C1-C6 anilino; and the substituents optionally present on R and R' are each independently selected from one or more of C1-C3 alkyl, C1-C3 alkoxy and halogen.

[0024] In the present invention, preferably, the substituents optionally present on R and R' are each independently selected from one or more of methyl, methoxy, -F, -Cl and -Br. Specifically,

[0025] Preferably, the substituent of the alkane is selected from one or more of methyl, methoxy, -F, -Cl and -Br.

[0026] Preferably, the substituents of the heteroaryl group are selected from one or more of methyl, methoxy, -F, -Cl and -Br.

[0027] Preferably, the substituents of the aryl group are selected from one or more of methyl, methoxy, -F, -Cl and -Br.

[0028] Preferably, the substituent of the olefin is selected from one or more of methyl, methoxy, -F, -Cl and -Br.

[0029] Preferably, the substituent of the anilino group is selected from one or more of methyl, methoxy, -F, -Cl and -Br.

[0030] In the present invention, preferably, the heteroatom of the heteroaryl group is a nitrogen atom.

[0031] In the present invention, preferably, R is a tert-butyl group or a trifluoromethyl group.

[0032] In the present invention, preferably, R' is a hydrogen atom, a trifluoromethyl group or a diphenylamino group.

[0033] In the present invention, preferably, the cyclometallated bisacetylene platinum (II) complex represented by formula (1) is

[0034]

[0035] The second aspect of the present invention provides a method for preparing a cyclometallated bisacetylene platinum (II) complex, comprising: contacting a compound represented by formula (2) with a compound represented by formula (3) in an inert atmosphere in the presence of an alkaline substance, a catalyst and a solvent,

[0036]

[0037] Wherein, R is selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 heteroaryl, substituted or unsubstituted C1-C6 aryl, or -SO3Na; R' is selected from hydrogen, substituted or unsubstituted C1-C6 alkane, substituted or unsubstituted C1-C6 alkene, or substituted or unsubstituted C1-C6 anilino; and the substituents optionally present on R and R' are each independently selected from one or more of C1-C3 alkyl, C1-C3 alkoxy and halogen.

[0038] According to the method of the present invention, preferably, the substituents optionally present on R and R' are each independently selected from one or more of methyl, methoxy, -F, -Cl and -Br. Specifically,

[0039] Preferably, the substituent of the alkane is selected from one or more of methyl, methoxy, -F, -Cl and -Br.

[0040] Preferably, the substituents of the heteroaryl group are selected from one or more of methyl, methoxy, -F, -Cl and -Br.

[0041] Preferably, the substituents of the aryl group are selected from one or more of methyl, methoxy, -F, -Cl and -Br.

[0042] Preferably, the substituent of the olefin is selected from one or more of methyl, methoxy, -F, -Cl and -Br.

[0043] Preferably, the substituent of the anilino group is selected from one or more of methyl, methoxy, -F, -Cl and -Br.

[0044] According to the method of the present invention, preferably, the heteroatom of the heteroaryl group is a nitrogen atom.

[0045] According to the method of the present invention, preferably, R is tert-butyl or trifluoromethyl.

[0046] According to the method of the present invention, preferably, R' is a hydrogen atom, a trifluoromethyl group or a diphenylamino group.

[0047] According to the method of the present invention, preferably, the compound represented by formula (2) is In the present invention, the compound represented by formula (2) can be prepared according to the literature (J. Med. Chem. 2004, 47, 2926-2934).

[0048] According to the method of the present invention, preferably, the compound represented by formula (3) is (2,2"-diethynyl-1,1':3',1'-terphenyl), (2,2"-diethynyl-5'-(trifluoromethyl)-1,1':3',1"-terphenyl) or (2,2"-diethynyl-N,N-diphenyl-[1,1':3',1"-terphenyl]-5'-amine).

[0049] In the present invention, It can be prepared according to the literature (J.Am.Chem.Soc, 2016, 138, 4726-4729).

[0050] According to the method of the present invention, preferably, the alkaline substance is one or more of diisopropylamine, triethylamine and morpholine, more preferably diisopropylamine.

[0051] According to the method of the present invention, the catalyst is preferably a CH bond activation catalyst, more preferably an anhydrous CH bond activation catalyst, and further preferably, the catalyst is cuprous acetate or cuprous iodide, more preferably cuprous iodide, such as anhydrous cuprous acetate or anhydrous cuprous iodide.

[0052] According to the method of the present invention, the solvent may be an anhydrous solvent, preferably, the organic solvent is one or more of acetonitrile, dimethyl sulfoxide and N,N-dimethylformamide, more preferably N,N-dimethylformamide, such as anhydrous acetonitrile, anhydrous dimethyl sulfoxide, anhydrous N,N-dimethylformamide.

[0053] According to the method of the present invention, preferably, the molar ratio of the compound represented by formula (2), the compound represented by formula (3), the alkaline substance and the catalyst is 1: (0.5-5): (80-150): (0.01-0.5): preferably 1: (1-3): (100-110): (0.05-0.2).

[0054] According to the method of the present invention, the amount of the solvent can be adjusted within a wide range. For example, the amount of the solvent is such that the concentration of the compound represented by formula (2) in the initial reaction is 0.005-0.05 mmol / mL, preferably 0.01-0.05 mmol / mL.

[0055] According to the method of the present invention, preferably, the contacting conditions include: a temperature of 10-50°C, preferably 20-30°C.

[0056] According to the method of the present invention, preferably, the contacting conditions include: a time of 12-48 hours, preferably 16-24 hours.

[0057] According to the method of the present invention, preferably, the contacting pressure is normal pressure, that is, the contacting is carried out under standard atmospheric pressure.

[0058] According to the method of the present invention, the inert atmosphere is intended to provide a suitable reaction environment for the reaction. Preferably, the inert atmosphere is nitrogen and / or argon. Further preferably, the inert atmosphere is dry nitrogen and / or dry argon.

[0059] According to the method of the present invention, preferably, the method further comprises: separating the product after contacting. The separation process can be carried out according to conventional purification methods in the art, such as column chromatography, distillation extraction and ether recrystallization, etc., preferably ether recrystallization.

[0060] According to the method of the present invention, the contacting can be carried out in a common device, such as a pressure tube, under the protection of nitrogen and / or argon.

[0061] According to the method of the present invention, the order of adding the compound represented by formula (2), the compound represented by formula (3), the alkaline substance, the catalyst and the solvent is not particularly limited, as long as all of them are added before the start of stirring.

[0062] The third aspect of the present invention provides a cyclometallated bisacetylene platinum (II) complex prepared by the above method.

[0063] The cyclometallated bisacetylene platinum (II) complex is preferably

[0064]

[0065] The fourth aspect of the present invention provides the use of the above-mentioned cyclometallated bisacetylene platinum (II) complex.

[0066] For example, the Pt(II) complex can show unique emission properties in the solid state, such as color change, mechanical coloration, etc. It can be used as a luminescent material in OLED applications, and can also be used as a dopant material and a color adjustment material, and the material has a long service life.

[0067] As another example, the above-mentioned Pt(II) complexes have improved stability and solubility under physiological conditions.

[0068] The application of the above-mentioned cyclometallated bisacetylene platinum (II) complex is not limited thereto.

[0069] The present invention will be described in detail below through examples.

[0070] In the following embodiments, Prepared according to the literature (J. Med. Chem. 2004, 47, 2926-2934).

[0071] (2,2"-diethynyl-1,1':3',1'-terphenyl), (2,2"-diethynyl-5'-(trifluoromethyl)-1,1':3',1"-terphenyl) and (2,2"-diethynyl-N,N-diphenyl-[1,1':3',1"-terphenyl]-5'-amine), prepared according to the literature (J. Am. Chem. Soc, 2016, 138, 4726-4729).

[0072] Diisopropylamine, triethylamine, anhydrous cuprous acetate, anhydrous cuprous iodide, anhydrous N,N-dimethylformamide, anhydrous acetonitrile and anhydrous dimethyl sulfoxide were purchased from J&K Technology Co., Ltd.

[0073] The present invention uses NMR spectrum and high-resolution mass spectrometry to test the structure of the complex prepared in the embodiment, wherein the NMR spectrum is measured by a Varian-Mercury 400MHz superconducting nuclear magnetic resonance instrument, wherein the deuterated reagent is deuterated chloroform (CDCl3), the hydrogen spectrum and carbon spectrum are based on tetramethylsilane as the internal standard, the phosphorus spectrum is based on 85% phosphoric acid, and the fluorine spectrum is based on 47% boron trifluoride ether solution. The high-resolution mass spectrum is measured by a Varian 7.0T FTMS high-resolution mass spectrometer.

[0074] Unless otherwise stated, all reagents and solvents used in the present invention were purified by standard methods (see the Reagent Purification Manual) before use.

[0075] In the following examples, the yield of the cyclometallated bisacetylene platinum (II) complex is calculated according to the following formula (I):

[0076] The yield of the cyclometallated bisacetylene platinum (II) complex (%) = (the actual yield of the cyclometallated bisacetylene platinum (II) complex / the theoretical yield of the cyclometallated bisacetylene platinum (II) complex) × 100% (Formula I)

[0077] Example 1

[0078] This example is used to illustrate the preparation of a cyclometallated bisacetylene platinum (II) complex.

[0079] Under a dry nitrogen atmosphere, (50 mg, 0.07 mmol), (39 mg, 0.14 mmol), diisopropylamine (1 mL, 722 mg, 7.14 mmol), anhydrous cuprous iodide (1 mg, 0.007 mmol) and anhydrous N,N-dimethylformamide (5 mL) were mixed in a pressure tube and stirred at room temperature for 30 minutes. The resulting suspension was stirred at room temperature for 24 hours and then filtered. After the filter cake was rinsed with ether, the filter cake was recrystallized in ether and separated to obtain a red solid product with a yield of 78% (50 mg). The product was analyzed and the results were as follows:

[0080] 1 H NMR (400MHz, DMSO) δ9.51 (d, J = 5.8 Hz, 2H), 9.21 (s, 2H), 8.65 (s, 1H), 8.31 (d, J = 7.7 Hz, 5H), 8.02 (d, J = 8.3Hz, 4H), 7.53 (dd, J = 15.0, 7.3Hz, 4H), 7.29 (d, J = 5.9Hz, 8H). 19 F NMR(376MHz,DMSO)δ-61.20.HRMS(ESI):m / z:[M+H] + calculated for C 46 H 27 N2F6Pt:916.1721; found:916.1721.

[0081] Example 2

[0082] This example is used to illustrate the preparation of a cyclometallated bisacetylene platinum (II) complex.

[0083] Under dry nitrogen protection, (50 mg, 0.07 mmol), (48 mg, 0.14 mmol), diisopropylamine (1 mL, 722 mg, 7.14 mmol), anhydrous cuprous iodide (1 mg, 0.007 mmol) and anhydrous N,N-dimethylformamide (5 mL) were mixed in a pressure tube and stirred at room temperature for 30 minutes. The resulting suspension was stirred at room temperature for 24 hours and then filtered. After the filter cake was rinsed with ether, the filter cake was recrystallized in ether and separated to obtain a red solid product with a yield of 77% (53 mg). The product was analyzed and the results were as follows:

[0084] 1 H NMR (400MHz, DMSO) δ9.49(d,J=5.8Hz,2H),9.21(s,2H),8.83(s,1H),8.31(d,J=7.6Hz,5H),8.02(d,J=8.3Hz,4H),7.58(d,J=7.8Hz,4H),7.33(m,7H). 19 F NMR(376MHz,DMSO)δ-60.75,-61.20.HRMS(ESI):m / z:[M+H] + calculated for C 47 H 26 N2F9Pt:984.1595; found:984.1587.

[0085] Example 3

[0086] This example is used to illustrate the preparation of a cyclometallated bisacetylene platinum (II) complex.

[0087] Under dry nitrogen protection, (50mg, 0.07mmol, (62 mg, 0.14 mmol), diisopropylamine (1 mL, 722 mg, 7.14 mmol), anhydrous cuprous iodide (1 mg, 0.007 mmol) and anhydrous N,N-dimethylformamide (5 mL) were mixed in a pressure tube and stirred at room temperature for 30 minutes. The resulting suspension was stirred at room temperature for 24 hours and then filtered. After the filter cake was rinsed with ether, the filter cake was recrystallized in ether and separated to obtain a red solid product with a yield of 53% (40 mg). The product was analyzed and the results were as follows:

[0088] 1H NMR (400MHz, DMSO) δ9.53(d,J=6.0Hz,2H),9.23(s,2H),8.44(s,1H),8.32(d,J=8.1Hz,5H),8.03(d,J=8.3Hz,4H),7.54(d, J=7.5Hz,2H),7.36–7.31(m,4H),7.29–7.24(m,3H),7.22–7.16(m,4H),7.16–7.11(m,4H),7.08–7.03(m,2H),6.89(s,2H). 19 F NMR(376MHz,DMSO)δ-61.22.HRMS(ESI):m / z:[M+H] + calculated for C 58 H 36 N3F6Pt:1083.2456; found:1083.2437.

[0089] Example 4

[0090] This example is used to illustrate the preparation of a cyclometallated bisacetylene platinum (II) complex.

[0091] Under dry nitrogen protection, (48 mg, 0.07 mmol), (39 mg, 0.14 mmol), diisopropylamine (1 mL, 722 mg, 7.14 mmol), anhydrous cuprous iodide (1 mg, 0.007 mmol) and anhydrous N,N-dimethylformamide (5 mL) were mixed in a pressure tube and stirred at room temperature for 30 minutes. The resulting suspension was stirred at room temperature for 24 hours and then filtered. After the filter cake was rinsed with ether, the filter cake was recrystallized in ether and separated to obtain a yellow solid product with a yield of 85% (55 mg). The product was analyzed and the results were as follows:

[0092] 1 H NMR (400MHz, DMSO) δ9.42(d,J=5.9Hz,2H),9.11(s,2H),8.67(s,1H),8.22(d,J=4.2Hz,2H),8.05(d,J=8. 4Hz,4H),7.65(d,J=8.5Hz,4H),7.56–7.50(m,4H),7.30–7.26(m,7H)1.36(s,18H).HRMS(ESI):m / z:[M+H] + calculated for C 52 H 45N2Pt:892.3235; found:892.3229.

[0093] Example 5

[0094] This example is used to illustrate the preparation of a cyclometallated bisacetylene platinum (II) complex.

[0095] Under dry nitrogen protection, (50 mg, 0.07 mmol), (48 mg, 0.14 mmol), diisopropylamine (1 mL, 722 mg, 7.14 mmol), anhydrous cuprous iodide (1 mg, 0.007 mmol) and anhydrous N,N-dimethylformamide (5 mL) were mixed in a pressure tube and stirred at room temperature for 30 minutes. The resulting suspension was stirred at room temperature for 24 hours and then filtered. After the filter cake was rinsed with ether, the filter cake was recrystallized in ether and separated to obtain a yellow solid product with a yield of 74% (52 mg). The product was analyzed and the results were as follows:

[0096] 1 H NMR(400MHz,DMSO)δ9.40(d,J=5.9Hz,2H),9.11(s,2H),8.84(s,1H),8.21(d,J=5.7Hz,2H),8.04 (d,J=8.4Hz,4H),7.65(d,J=8.4Hz,4H),7.58(d,J=8.7Hz,4H),7.38–7.28(m,6H),1.36(s,18H). 19 F NMR(376MHz,DMSO)δ-60.75.HRMS(ESI):C 53 H 44 N2F3Pt:960.3098; found:960.3099.

[0097] Example 6

[0098] This example is used to illustrate the preparation of a cyclometallated bisacetylene platinum (II) complex.

[0099] Under dry nitrogen protection, (50 mg, 0.07 mmol), (62 mg, 0.14 mmol), diisopropylamine (1 mL, 722 mg, 7.14 mmol), anhydrous cuprous iodide (1 mg, 0.007 mmol) and anhydrous N,N-dimethylformamide (5 mL) were mixed in a pressure tube and stirred at room temperature for 30 minutes. The resulting suspension was stirred at room temperature for 24 hours and then filtered. After the filter cake was rinsed with ether, the filter cake was recrystallized in ether and separated to obtain a yellow solid product with a yield of 55% (42 mg). The product was analyzed and the results were as follows:

[0100] 1 H NMR(400MHz,DMSO)δ9.44(d,J=5.9Hz,2H),9.12(s,2H),8.45(s,1H),8.23(d ,J=5.9Hz,2H),8.06(d,J=8.5Hz,4H),7.66(d,J=8.5Hz,4H),7.54(d,J=7.6H z,2H),7.33(t,J=7.9Hz,4H),7.26(t,J=7.5Hz,2H),7.21–7.11(m,8H),7.06 (t,J=7.3Hz,2H),6.89(d,J=1.4Hz,2H),1.37(s,18H).HRMS(ESI):m / z:[M+H] + calculated for C 54 H 54 N3Pt:1059.3960; found:1059.3951.

[0101] Example 7

[0102] This example is used to illustrate the preparation of a cyclometallated bisacetylene platinum (II) complex.

[0103] Under a dry nitrogen atmosphere, (50 mg, 0.07 mmol), (597.5 mg, 0.35 mmol), triethylamine (1.46 mL, 1062 mg, 10.5 mmol), anhydrous cuprous acetate (0.4 mg, 0.0035 mmol) and anhydrous acetonitrile (5 mL) were mixed in a pressure tube and stirred at room temperature for 30 minutes. The resulting suspension was stirred at room temperature for 30 hours and then filtered. After the filter cake was rinsed with ether, the filter cake was recrystallized in ether and separated to obtain a red solid product with a yield of 60% (38 mg). The product was analyzed and the results were as follows:

[0104] 1H NMR (400MHz, DMSO) δ9.51 (d, J = 5.8 Hz, 2H), 9.21 (s, 2H), 8.65 (s, 1H), 8.31 (d, J = 7.7 Hz, 5H), 8.02 (d, J = 8.3Hz, 4H), 7.53 (dd, J = 15.0, 7.3Hz, 4H), 7.29 (d, J = 5.9Hz, 8H). 19 F NMR(376MHz,DMSO)δ-61.20.HRMS(ESI):m / z:[M+H] + calculated for C 46 H 27 N2F6Pt:916.1721; found:916.1721.

[0105] Example 8

[0106] This example is used to illustrate the preparation of a cyclometallated bisacetylene platinum (II) complex.

[0107] Under a dry nitrogen atmosphere, (50 mg, 0.07 mmol), (97.5 mg, 0.35 mmol), morpholine (0.49 mL, 487.9 mg, 5.6 mmol), anhydrous cuprous acetate (4 mg, 0.035 mmol) and anhydrous dimethyl sulfoxide (5 mL) were mixed in a pressure tube and stirred at room temperature for 30 minutes. The resulting suspension was stirred at room temperature for 16 hours and then filtered. After the filter cake was rinsed with ether, the filter cake was recrystallized in ether and separated to obtain a red solid product with a yield of 67% (43 mg). The product was analyzed and the results were as follows:

[0108] 1 H NMR (400MHz, DMSO) δ9.51 (d, J = 5.8 Hz, 2H), 9.21 (s, 2H), 8.65 (s, 1H), 8.31 (d, J = 7.7 Hz, 5H), 8.02 (d, J = 8.3Hz, 4H), 7.53 (dd, J = 15.0, 7.3Hz, 4H), 7.29 (d, J = 5.9Hz, 8H). 19 F NMR(376MHz,DMSO)δ-61.20.HRMS(ESI):m / z:[M+H] + calculated for C 46 H 27 N2F6Pt:916.1721; found:916.1721.

[0109] It can be seen from the above examples that the method of the present invention can be used to prepare the cyclometallated bisacetylene platinum (II) complex with simple process, mild reaction conditions and high yield.

[0110] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A cyclometallated bis-acetylene platinum (II) complex, characterized in that: The platinum (II) complex has a structure shown in formula (1), Formula (1), Wherein, R is selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 aryl, or -SO3Na; R' is selected from hydrogen, substituted or unsubstituted C1-C6 alkane, or substituted or unsubstituted C1-C6 anilino; the optional substituents on R and R' are each independently selected from one or more of C1-C3 alkyl, C1-C3 alkoxy and halogen.

2. The cyclometallated bisacetylene platinum (II) complex according to claim 1, wherein The optional substituents on R and R' are each independently selected from one or more of methyl, methoxy, -F, -Cl and -Br.

3. The cyclometallated bisacetylene platinum (II) complex according to claim 1 or 2, wherein R is a tert-butyl group or a trifluoromethyl group; R' is a hydrogen atom, a trifluoromethyl group or a diphenylamino group.

4. A method for preparing a cyclometallated bis-acetylene platinum (II) complex, comprising: Under an inert atmosphere, in the presence of a basic substance, a catalyst and a solvent, the compound represented by formula (2) is contacted with the compound represented by formula (3), Formula (2), Formula (3), Wherein, R is selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 aryl, or -SO3Na; R' is selected from hydrogen, substituted or unsubstituted C1-C6 alkane, or substituted or unsubstituted C1-C6 anilino; the substituents optionally present on R and R' are each independently selected from one or more of C1-C3 alkyl, C1-C3 alkoxy and halogen; The molar ratio of the compound represented by formula (2), the compound represented by formula (3), the alkaline substance and the catalyst is 1: (0.5-5): (80-150): (0.01-0.5).

5. The platinum (II) complex according to claim 4, wherein The optional substituents on R and R' are each independently selected from one or more of methyl, methoxy, -F, -Cl and -Br.

6. The platinum (II) complex according to claim 5, wherein R is a tert-butyl group or a trifluoromethyl group; R' is a hydrogen atom, a trifluoromethyl group or a diphenylamino group.

7. The platinum (II) complex according to claim 6, wherein The compound represented by formula (2) is or ; And / or, the compound represented by formula (3) is , or .

8. The method according to any one of claims 4 to 7, wherein: The alkaline substance is one or more of diisopropylamine, triethylamine and morpholine.

9. The method according to claim 8, wherein: The alkaline substance is diisopropylamine.

10. The method according to any one of claims 4 to 7 and 9, wherein: The catalyst is cuprous acetate or cuprous iodide.

11. The method according to claim 10, wherein: The catalyst is cuprous iodide.

12. The method according to any one of claims 4 to 7, 9 and 11, wherein: The solvent is one or more of acetonitrile, dimethyl sulfoxide and N,N-dimethylformamide.

13. The method according to claim 12, wherein: The solvent is N,N-dimethylformamide.

14. The method according to any one of claims 4 to 7, 9, 11 and 13, wherein: The molar ratio of the compound represented by formula (2), the compound represented by formula (3), the alkaline substance and the catalyst is 1: (1-3): (100-110): (0.05-0.2).

15. The method according to any one of claims 4 to 7, 9, 11 and 13, wherein: The contact conditions include: temperature of 10-50° C.; time of 12-48 h.

16. The method according to claim 15, wherein: The contact conditions include: temperature of 20-30° C. and time of 16-24 h.

17. The method according to any one of claims 4 to 7, 9, 11, 13 and 16, wherein: The method further comprises: separating the contacted product; Wherein, the separation is one or more of column chromatography, distillation extraction and ether recrystallization.

18. The method according to claim 17, wherein: The separation was performed by recrystallization from diethyl ether.

19. Use of the cyclometallated bisacetylene platinum (II) complex according to any one of claims 1 to 3 in OLED.

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