A meta-phenyl bridged alkynyl pyrazole pyridine derivative and its preparation method and application

Abstract

The present invention discloses an m-phenyl bridged alkynylpyrazole pyridine derivative and its preparation method and application, belonging to the technical field of pyrazole pyridine derivatives. The preparation method of the m-phenyl bridged alkynylpyrazole pyridine derivative comprises dissolving a pyrazole halide, an acetylene aromatic compound, and a catalyst in a solvent, heating and refluxing under an N2 atmosphere, filtering, spin-drying, and chromatographic evaporation to obtain a solid product; adding the solid product to a mixed solvent of methanol and dichloromethane in a volume ratio of 1:1, adding HCl to the mixed solvent to remove the protecting group, adding NaHCO3 to adjust the pH of the mixed solvent to 7, filtering to obtain a solid, and washing, filtering, and vacuum drying the solid to obtain a derivative. The m-phenyl bridged alkynylpyrazole pyridine derivative and its preparation method and application described in the present invention can solve the problems of the simple coordination form of the single pyridine pyrazole ligand used in the prior art and the single structure and function of the resulting complex.

Description

Technical Field

[0001] The present invention relates to the technical field of pyrazole and pyridine derivatives, in particular to an m-phenyl bridged alkynyl pyrazole and pyridine derivative, a preparation method and application thereof. Background Art

[0002] Pyrazole ligands are a relatively complex class of multifunctional organic bridging ligands, and their supramolecular assemblies have good application value in catalysis, magnetism, molecular recognition, ion sensing, photophysical properties, etc. At the same time, supramolecular self-assembly driven by transition metal-directed coordination in the pyridine system has become a research hotspot in recent years due to its good guidance and suitable chemical bond energy.

[0003] Existing technologies typically utilize individual pyrazole or pyridine ligands, which often undergo a one-step reaction, produce relatively simple products, and lack controllability. Therefore, it is particularly important to design pyrazole and pyridine ligands with different functions into a single ligand, employing a programmed hierarchical self-assembly strategy. Furthermore, the weak π-interaction between alkynyl groups and metal cations provides favorable conditions for the formation of novel supramolecular structures. This strategy can yield supramolecular systems with more novel structures and tunable functions by controlling the selection of different metal centers in the secondary assembly. Summary of the Invention

[0004] The present invention aims to provide an m-phenyl bridged alkynylpyrazole-pyridine derivative and its preparation method and application, so as to solve the problems in the prior art that the coordination form of the single pyridine-pyrazole ligand is simple and the structure and function of the resulting complex are single.

[0005] To achieve the above objectives, the present invention provides an m-phenyl bridged alkynyl pyrazole pyridine derivative, the chemical structure of which is:

[0006]

[0007] R1 is -H or

[0008] R2 is

[0009] The preparation method of the above-mentioned m-phenyl bridged alkynyl pyrazole pyridine derivative comprises the following steps:

[0010] S1, dissolving a pyrazole halide, an ethynyl aromatic compound, and a catalyst in a solvent, heating under reflux under a N2 atmosphere, filtering, spin-drying, and chromatographically evaporating to obtain a solid product;

[0011] S2. The solid product is added to a mixed solvent of methanol and dichloromethane in a volume ratio of 1:1, HCl is added to the mixed solvent to remove the protecting group, NaHCO3 is added to adjust the pH of the mixed solvent to 7, and a solid is obtained after filtration. The solid is washed, filtered, and vacuum-dried to obtain a derivative.

[0012] Preferably, in S1, the pyrazole halide is 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, the ethynyl aromatic compound is 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, the catalyst is tetrakistriphenylphosphine palladium and cuprous iodide, and the solvent is triethylamine and toluene;

[0013] 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, tetrakistriphenylphosphine palladium, cuprous iodide, and a 1 MOL / L tetrabutylammonium fluoride tetrahydrofuran solution were dissolved in triethylamine and toluene, and the mixture was heated under reflux at 50° C.-80° C. for 8-15 hours under a nitrogen atmosphere, filtered, and dried at 40° C.-60° C., chromatographed, and rotary evaporated to obtain a solid product.

[0014] The molar ratio of 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole to 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is 1:1.0-1.2, and the molar ratio of 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine to a 1 MOL / L tetrabutylammonium fluoride solution in tetrahydrofuran is 1:1.0-1.5. The eluent for chromatography is a mixture of petroleum ether and ethyl acetate in a volume ratio of 2-5:1;

[0015] In the S2, R1 is -H, and R2 is derivatives of .

[0016] Preferably, in S1, the pyrazole halide is 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole, the ethynyl aromatic compound is 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, the catalyst is tetrakistriphenylphosphine palladium and cuprous iodide, and the solvent is triethylamine and toluene;

[0017] 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole, 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, tetrakistriphenylphosphine palladium, cuprous iodide, and a 1 MOL / L tetrabutylammonium fluoride tetrahydrofuran solution were dissolved in triethylamine and toluene, and the mixture was heated under reflux at 50° C.-80° C. for 8-15 hours under a nitrogen atmosphere, filtered, and dried at 40° C.-60° C., chromatographed, and rotary evaporated to obtain a solid product;

[0018] The molar ratio of 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole and 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is 1:1.0-1.2, and the molar ratio of 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine to a 1 MOL / L tetrabutylammonium fluoride solution in tetrahydrofuran is 1:1.0-1.5. The eluent for chromatography is a mixture of petroleum ether and ethyl acetate in a volume ratio of 2-5:1;

[0019] The R1 obtained in S2 is R2 is derivatives of .

[0020] Preferably, the preparation method of the 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is:

[0021] (3-Bromophenylethynyl)trimethylsilane, 3-ethynylpyridine, tetrakistriphenylphosphine palladium, and cuprous iodide are dissolved in triethylamine and toluene, and the mixture is stirred at 60°C-90°C under a nitrogen atmosphere for 12-18 hours. The mixture is filtered through diatomaceous earth, dried by spin drying, chromatographed, and rotary evaporated to obtain 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine; the molar ratio of (3-bromophenylethynyl)trimethylsilane to 3-ethynylpyridine is 1:1.0-1.2; and the eluent for chromatography is pure dichloromethane.

[0022] Preferably, the preparation method of the 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole is:

[0023] 4-Ethyl-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole, 1,3-dibromo-5-iodobenzene, bistriphenylphosphine palladium dichloride, and cuprous iodide were dissolved in triethylamine, heated under reflux at 35°C-45°C under N2 atmosphere for 8-15 hours, filtered through celite, dried at 40°C-60°C, chromatographed, and rotary evaporated to obtain 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole;

[0024] The molar ratio of 1,3-dibromo-5-iodobenzene and 4-ethyl-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole is 1:1.0-1.2, and the eluent during chromatography is a mixture of petroleum ether and ethyl acetate in a volume ratio of 8-15:1.

[0025] Preferably, in S1, the pyrazole halide is 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, the ethynyl aromatic compound is 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, the catalyst is tetrakistriphenylphosphine palladium and cuprous iodide, and the solvent is triethylamine and toluene;

[0026] 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, tetrakistriphenylphosphine palladium, cuprous iodide, and a 1 MOL / L tetrabutylammonium fluoride tetrahydrofuran solution were dissolved in triethylamine and toluene, and the mixture was heated under reflux at 50° C.-80° C. for 8-15 hours under a nitrogen atmosphere, filtered, and dried at 40° C.-60° C., chromatographed, and rotary evaporated to obtain a solid product;

[0027] The molar ratio of 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole to 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is 1:1.0-1.2, and the molar ratio of 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine to a 1 MOL / L tetrabutylammonium fluoride solution in tetrahydrofuran is 1:1.0-1.5. The eluent for chromatography is a mixture of petroleum ether and ethyl acetate in a volume ratio of 2-5:1;

[0028] In the S2, R1 is -H, and R2 is derivatives of .

[0029] Preferably, the preparation method of the 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is:

[0030] (3-Bromophenylethynyl)trimethylsilane, 4-ethynylpyridine, tetrakistriphenylphosphine palladium, and cuprous iodide are dissolved in triethylamine and toluene, and the mixture is stirred at 60°C-90°C under a nitrogen atmosphere for 12-18 hours. The mixture is filtered through diatomaceous earth, dried by spin drying, chromatographed, and rotary evaporated to obtain 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine; the molar ratio of (3-bromophenylethynyl)trimethylsilane to 4-ethynylpyridine is 1:1.0-1.2; and the eluent for chromatography is pure dichloromethane.

[0031] Preferably, in S1, the pyrazole halide is 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, the ethynyl aromatic compound is m-diethynylbenzene, the catalyst is tetrakistriphenylphosphine palladium and cuprous iodide, and the solvent is triethylamine;

[0032] 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole, m-diethynylbenzene, tetrakistriphenylphosphine palladium, and cuprous iodide were dissolved in triethylamine, heated under reflux at 40°C-50°C for 6-10 hours under N2 atmosphere, filtered, dried at 40°C-60°C, chromatographed, and rotary evaporated to obtain a solid product;

[0033] The molar ratio of 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole to m-diethynylbenzene was 1:2.21, and the eluent for chromatography was a mixture of dichloromethane and ethyl acetate in a volume ratio of 40:1;

[0034] In the S2, R1 is -H, and R2 is derivatives of .

[0035] The above-mentioned m-phenyl bridged alkynyl pyrazole pyridine derivatives are used in coordination chemistry, heavy metal ion detection, catalysis, and molecular machines.

[0036] The m-phenyl-bridged alkynylpyrazole-pyridine derivatives at different positions have different coordination angles. By designing them to coordinate with different metal ions to form compounds with different angles, shapes, and coordination numbers, materials with novel structures and good catalytic and sensing properties are obtained.

[0037] Pyrazole ligands are a class of organic ligands with bidentate coordination functions, which can form three coordination forms in supramolecular self-assembly: monodentate coordination, bidentate bridging and bidentate chelation. Compared with some monodentate ligands, the self-assembled molecules constructed by pyrazole ligands have more novel structures and richer functional properties. At the same time, the supramolecular self-assembly driven by transition metal-guided coordination of pyridine system has been applied to many synthetic fields due to its good guidance, suitable chemical bond energy and other advantages. The present invention designs pyrazole and pyridine into the same ligand, adopts programmed hierarchical self-assembly, and prepares a novel structural and functionally adjustable supramolecular structure by controlling the selection of different secondary assembly metal centers. At the same time, by introducing alkynyl groups to generate weak π interactions with metal cations, the assembly structure can be made more novel. The pyrazole and pyridine functional groups in the ligand can achieve selective recognition of metal cations through the metal-organic coordination of metal ions.

[0038] The advantages and positive effects of the m-phenyl bridged alkynyl pyrazole pyridine derivatives and their preparation methods and applications are as follows:

[0039] 1. The present invention incorporates pyrazole and pyridine into the same ligand, resulting in different coordination angles. By designing compounds that can coordinate with different metal ions to form compounds with varying angles, shapes, and coordination numbers, a novel structure with excellent catalytic and sensing properties is obtained. Furthermore, by introducing an alkynyl group to generate a weak π interaction with the metal cation, the assembly structure is further novel. The pyrazole and pyridine functional groups in the ligand, through metal-organic coordination with the metal ion, can achieve selective recognition of the metal cation.

[0040] 2. The preparation method of the present invention is simple to operate and involves only common organic synthesis steps; the production cost is low, and the raw materials are cheap and readily available; the yield is above 70%; the post-processing and purification are simple, and it is suitable for the industrial production of m-phenyl-bridged alkynylpyrazole and pyridine derivatives.

[0041] 3. The m-phenyl bridged alkynylpyrazole and pyridine derivatives of the present invention can be applied to coordination chemistry, heavy metal ion sensing, catalysis, molecular machines and other fields, and have a wide range of applications.

[0042] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 The synthetic route diagram of Example 1 to Example 4 of the present invention;

[0044] Figure 2 The crystal structure of the complex Ag-[(bpy)Pd]2(L)2(NO3)2-OTf is shown as viewed from the a-axis direction;

[0045] Figure 3 The crystal stacking structure of the complex Ag-[(bpy)Pd]2(L)2(NO3)2 is viewed from the a-axis direction;

[0046] Figure 4 The crystal stacking structure diagram of the complex Ag-[(bpy)Pd]2(L)2(NO3)2 viewed from the b-axis direction;

[0047] Figure 5 The crystal stacking structure of the complex Ag-[(bpy)Pd]2(L)2(NO3)2 is viewed from the c-axis direction;

[0048] Figure 6 The UV-visible absorption spectra of the complex [(bpy)Pd]2(L)2(NO3)2 mixed solution with the addition of different cations;

[0049] Figure 7 Add Hg to the complex [(bpy)Pd]2(L)2(NO3)2 solution 2+ and Hg2+ UV-visible absorption spectra of other cations. DETAILED DESCRIPTION

[0050] The embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0051] Example 1

[0052] An m-phenyl bridged alkynyl pyrazole pyridine derivative wherein R1 is -H and R2 is The structural formula of the derivative is:

[0053]

[0054] Synthesis circuit such as Figure 1 The specific steps are as follows:

[0055] S2. Dissolve 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole (1.65 g; 5.99 mmol), 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine (1.66 g; 5.97 mmol), tetrakistriphenylphosphine palladium (0.023 eq; 160 mg, 0.138 mmol), cuprous iodide (0.048 eq; 54 mg, 0.284 mmol), and tetrabutylammonium fluoride (1 MOL / L tetrahydrofuran solution, 6.1 mL) in triethylamine (20 mL) and toluene (10 mL), heat under reflux at 60 ° C under N2 atmosphere for 10 hours, filter with celite, spin-dry at 50 ° C, chromatograph (petroleum ether: ethyl acetate = 3:1), and rotary evaporation to obtain a solid product.

[0056] The preparation method of 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is:

[0057] (3-Bromophenylethynyl)trimethylsilane (7.02 mmol; 1.77 g), 3-ethynylpyridine (7.09 mmol; 730.97 mg), tetrakistriphenylphosphine palladium (0.025 eq; 0.176 mmol; 202.80 mg), and cuprous iodide (0.026 eq; 0.183 mmol; 34.76 mg) were dissolved in triethylamine (20 mL) and toluene (10 mL). The mixture was stirred at 80°C overnight under a nitrogen atmosphere, filtered through celite, and dried in a rotary evaporation at 50°C. The mixture was then chromatographed (dichloromethane) and rotary evaporated to give 1.66 g of 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine. The yield of 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine was 85%.

[0058] S2. Prepare a mixed solvent of 20 mL of methanol and 20 mL of dichloromethane, dissolve the solid product in the mixed solvent, add 1 mL of HCl to remove the protecting groups, adjust the pH to 7 by adding NaHCO3, filter to obtain a solid, wash the solid with a small amount of methanol, filter, and vacuum dry to obtain 1.14 g of Compound I. The yield of Compound I is 71%.

[0059] Example 2

[0060] An m-phenyl bridged alkynyl pyrazole pyridine derivative wherein R1 is -H and R2 is The structural formula of the derivative is:

[0061]

[0062] Synthesis circuit such as Figure 1 As shown, the specific synthesis steps are the same as those in Example 1, except that:

[0063] In step S1, 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine.

[0064] In the preparation process of 4-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, 3-ethynylpyridine is 4-ethynylpyridine.

[0065] The yield of compound II was 82%.

[0066] Example 3

[0067] An m-phenyl bridged alkynyl pyrazole pyridine derivative wherein R1 is R2 is The structural formula of the derivative is:

[0068]

[0069] Synthesis circuit such as Figure 1 The specific steps are as follows:

[0070] S1. Dissolve 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine (1.37 g; 4.98 mmol), 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole (1.00 g; 2.45 mmol), tetrakistriphenylphosphine palladium (0.026 eq; 147.22 mg, 0.127 mmol), cuprous iodide (0.025 eq; 37.71 mg, 0.198 mmol), and tetrabutylammonium fluoride (1 MOL / L tetrahydrofuran solution, 5.2 mL) in triethylamine (20 mL) and toluene (10 mL), heat under reflux at 60 ° C under N2 atmosphere overnight, filter with celite, spin-dry at 50 ° C, chromatograph (petroleum ether: ethyl acetate = 3:1), and rotary evaporation to obtain a solid product.

[0071] The preparation method of 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole is as follows:

[0072] 4-Ethyl-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole (1.15 g; 6.53 mmol), 1,3-dibromo-5-iodobenzene (2.28 g; 6.34 mmol), bistriphenylphosphine palladium dichloride (0.025 eq; 111.25 mg, 0.159 mmol), and cuprous iodide (0.026 eq; 31.39 mg, 0.165 mmol) were dissolved in triethylamine (30 mL), heated under reflux at 40 ° C. under N2 atmosphere for 9 hours, filtered through celite, dried at 50 ° C., chromatographed (petroleum ether: ethyl acetate = 10: 1), and rotary evaporated to give 2.25 mg of the intermediate product 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole. The yield of 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole was 87%.

[0073] S2. A mixed solvent of 20 mL of methanol and 20 mL of dichloromethane was prepared, and the solid product was dissolved in the mixed solvent. 1 mL of HCl was added to remove the protecting groups. NaHCO₃ was added to adjust the pH to 7, and the solid was filtered. A small amount of dichloromethane and a large amount of petroleum ether were added to the solid for recrystallization. The solid was filtered and dried under vacuum to obtain 985.67 mg of Compound III. The yield of Compound III was 70.5%.

[0074] Example 4

[0075] An m-phenyl bridged alkynyl pyrazole pyridine derivative wherein R1 is -H and R2 is The structural formula of the derivative is:

[0076]

[0077] Synthesis circuit such as Figure 1 The specific steps are as follows:

[0078] 4-iodo-1-(tetrahydropyran-2-yl)-1H-pyrazole (2.43 g; 8.74 mmol), m-diethynylbenzene (500 mg; 5.97 mmol), tetrakistriphenylphosphine palladium (0.012 eq; 109.82 mg, 0.095 mmol), and cuprous iodide (0.025 eq; 37.71 mg, 0.198 mmol) were dissolved in triethylamine (15 mL), heated to reflux at 45 ° C under N2 atmosphere for 8 hours, and then dried at 50 ° C. The product was chromatographed (dichloromethane: ethyl acetate = 40:1) and rotary evaporated to obtain a solid product.

[0079] A mixed solvent of 20 mL of methanol and 20 mL of dichloromethane was prepared, and the solid product was dissolved in the mixed solvent. 1 mL of HCl was added to remove the protecting groups. NaHCO₃ was added to adjust the pH to 7, and the solid was filtered. A small amount of methanol was added to wash the solid, and the solid was filtered and dried under vacuum to obtain 716 mg of Compound IV. The yield of Compound IV was 70%.

[0080] Experimental testing

[0081] (1) The nuclear magnetic resonance analysis results of the m-phenyl bridged alkynyl pyrazole pyridine derivatives prepared in Examples 1 to 4 are as follows:

[0082] Example 1 Compound Ⅰ:

[0083] 1 H NMR (400MHz, DMSO-d6, ppm) = 13.24 (br, 1H), 8.78 (s, 1H), 8.62 (d, J = 4.0Hz, 1H), 8.17 (s, 1 H), 8.01 (d, J = 8.0Hz, 1H), 7.77 (s, 1H), 7.69 (s, 1H), 7.60-7.54 (m, 2H), 7.50-7.46 (m, 2H).

[0084] Example 2 Compound II:

[0085] 1 H NMR (400MHz, DMSO-d6, ppm) = 13.26 (s, 1H), 8.65 (dd, J = 4.4, 1.6Hz, 2H), 8.18 (s, 1 H),7.77(s,1H),7.71(t,J=1.4Hz,1H),7.63–7.54(m,4H),7.50(t,J=7.7Hz,1H).

[0086] Example 3 Compound III:

[0087] 1 H NMR (400MHz, DMSO-d6, ppm) = 13.28 (s, 1H), 8.80 (s, 2H), 8.62 (d, J = 4.8Hz, 2H), 8.01 (t, J = 7.5Hz, 4H), 7.84 ( s,2H),7.78(s,1H),7.73(s,2H),7.67(d,J=7.7Hz,4H),7.55(t,J=7.7Hz,2H),7.50(dd,J=7.8,5.0Hz,2H).

[0088] Example 4 Compound IV:

[0089] 1 H NMR (400MHz, DMSO-d6, ppm) = 13.23 (s, 2H), 8.16 (s, 2H), 7.76 (s, 2H), 7.54 (s, 1H), 7.49–7.45 (m, 2H), 7.42 (dd, J = 9.1, 5.9Hz, 1H).

[0090] The nitrogen on the pyrazole and the nitrogen on the pyridine in the pyrazole-pyridine ligands have good coordination ability with metals, so a supramolecular structure is obtained by coordination with metals, as shown in the following (2) to (3):

[0091] (2) Compound I obtained in Example 1 was first assembled with bpyPd(NO3)2 to obtain a primary assembly through a hierarchical assembly strategy, and then assembled with silver nitrate and silver trifluoromethanesulfonate to obtain different topological structures. The specific operation includes the following steps:

[0092] a. The compound obtained in Example 1 was assembled with bpyPd(NO3)2, and the specific operation was as follows:

[0093] The compound (11.4 mg, 0.02 mmol) and bpyPd(NO3)2 (19.3 mg, 0.05 mmol) were dissolved in 1.0 mL DMSO-d6, assembled at 40°C, and the assembly was monitored by hydrogen nuclear magnetic resonance tracking.

[0094] The results of nuclear magnetic resonance analysis of the complex [(bpy)Pd]2(L)2(NO3)2 are:

[0095] 1H NMR (400MHz, DMSO, ppm) = 8.80 (d, J = 1.8Hz, 1H), 8.65 (dd, J = 4.8, 1.2Hz, 1H), 8.46 (s, 2H), 8.41 (s, 2H), 8.38 (s, 2H), 8.20 (d, J = 5. 0Hz,2H),8.04–8.00(m,1H),7.82(t,J=6.8Hz,2H),7.54(dd,J=7.7,5.0Hz,1H),7.42(d,J=27.0Hz,2H),7.19(s,1H),7.04(s,1H).

[0096] b. Dissolve the primary assembly [(bpy)Pd]2(L)2(NO3)2 (14.82 mg, 0.125 mmol) and AgOTf (3.21 mg, 0.0125 mmol) in 1.0 mL of DMSO-d6. Stir at room temperature for 30 minutes and at 40°C for 1 hour. Diffuse the solution with ethyl acetate, a poor solvent. Block crystals are obtained after 5 days. The assembly is monitored by H NMR.

[0097] The results of the nuclear magnetic resonance analysis of the complex Ag-[(bpy)Pd]2(L)2(NO3)2-OTf are as follows:

[0098] 1 H NMR (400MHz, DMSO-d6, ppm) = 8.80 (s, 4H), 8.65 (d, J = 4.6Hz, 5H), 8.54–8.31 (m, 22H), 8.20 (d, J = 5.2Hz, 7H), 8.0 3(d,J=7.9Hz,4H),7.82(t,J=6.5Hz,7H),7.59–7.51(m,5H),7.40(d,J=20.0Hz,7H),7.17(s,4H),7.02(s,3H).

[0099] The crystal structure of the complex Ag-[(bpy)Pd]2(L)2(NO3)2-OTf is as follows Figure 2 shown.

[0100] c. Dissolve the primary assembly [(bpy)Pd]2(L)2(NO3)2 (23.72 mg, 0.02 mmol) and AgNO3 (3.40 mg, 0.02 mmol) in 1.0 mL of DMSO-d6 and stir at room temperature for 30 min and at 40°C for 1 h. Add ethyl acetate to precipitate the solid, centrifuge, dry, and dissolve in a 1:1 mixture of acetonitrile and methanol. Diffuse the solid with isopropyl ether, a poor solvent, into the solution. After 2 days, block crystals were obtained. The assembly was monitored by H NMR spectroscopy.

[0101] The results of nuclear magnetic resonance analysis of the complex Ag-[(bpy)Pd]2(L)2(NO3)2-NO3 are as follows:

[0102] 1 H NMR (400MHz, DMSO-d6, ppm) = 8.88 (s, 6H), 8.72 (s, 9H), 8.41 (s, 28H), 8.19 ( s,15H),7.80(s,10H),7.66(s,10H),7.41(s,10H),7.07(d,J=74.3Hz,7H).

[0103] The crystal structure of the complex Ag-[(bpy)Pd]2(L)2(NO3)2-NO3 is as follows Figure 3 、 Figure 4 、 Figure 5 shown.

[0104] Example 3: Compound II I obtained and assembled with bpyPd(NO3)2

[0105] (3) Compound II obtained in Example 3 was assembled with bpyPd(NO3)2, and the specific operation was as follows:

[0106] Compound II (11.4 mg, 0.02 mmol) and bpyPd(NO3)2 (7.73 mg, 0.02 mmol) were dissolved in 0.7 mL DMSO-d6, assembled at 40°C, and the assembly was monitored by hydrogen nuclear magnetic resonance tracking.

[0107] The results of nuclear magnetic resonance analysis of complex II are:

[0108] 1 H NMR (400MHz, DMSO, ppm) = 9.48 (d, J = 39.4Hz, 3H), 9.33 (s, 3H), 9.10 (s, 3H), 8.81 (s, 9H), 8.69 (s, 4H), 8.63 (s, 7H), 8.47 (d, J = 34.1Hz, 29H), 8.25 (d ,J=27.9Hz,19H),8.02(d,J=7.1Hz,8H),7.84(s,26H),7.71(dd,J=23.2, 5.5Hz,26H),7.65–7.57(m,11H),7.49(s,12H),7.33(s,7H),7.21(s,2H).

[0109] (4) UV test was conducted on the complex [(bpy)Pd]2(L)2(NO3)2.

[0110] The complex [(bpy)Pd]2(L)2(NO3)2 was dissolved in DMSO at a concentration of 10 μM. 2 mL of the mixed solution was added with 5 μL of the cation (Cd 2+ 、Co 2+ 、Hg 2+ , K + 、Li + Mg 2+ 、Mn 2+ 、Na + 、Ni 2+ 、Zn 2+ ) were tested in parallel, with a cation solution concentration of 0.1 M. Hg was then added to the DMSO solution. 2+ It was found that Hg could still be detected in the presence of other ions. 2+ . Figure 6 The UV-visible absorption spectra of the complex [(bpy)Pd]2(L)2(NO3)2 mixed solution with the addition of different cations; Figure 7 The complex [(bpy)Pd]2(L)2(NO3)2 and Hg 2+ The UV-visible absorption spectrum of other cations added to the mixed solution. Figure 6 、 Figure 7 As shown, only the addition of Hg 2+ It shows obvious UV absorption enhancement, indicating that the structure can single recognize Hg 2+ .

[0111] Therefore, the present invention utilizes the aforementioned m-phenyl-bridged alkynylpyrazol-pyridine derivative, its preparation method, and its application. The preparation method has few steps and is simple to operate, involving only common organic synthesis steps. It also has low production costs, uses inexpensive and readily available raw materials, and produces yields exceeding 70%. Post-processing and purification are simple, making it suitable for industrial production of m-phenyl-bridged alkynylpyrazol-pyridine derivatives. The m-phenyl-bridged alkynylpyrazol-pyridine derivatives described in the present invention address the problems of the existing art, which suffer from the simple coordination structure of the individual pyridine-pyrazole ligands and the resulting complexes having a single structure and function.

[0112] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the same. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solutions of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. An m-phenyl bridged alkynyl pyrazole pyridine derivative, characterized in that: Its chemical structural formula is: 。 2. A method for preparing an m-phenyl bridged alkynylpyrazole-pyridine derivative according to claim 1, characterized in that: 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole, 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine, tetrakistriphenylphosphine palladium, cuprous iodide, and a 1 MOL / L tetrabutylammonium fluoride tetrahydrofuran solution were dissolved in triethylamine and toluene, and the mixture was heated under reflux at 50° C.-80° C. for 8-15 hours under a nitrogen atmosphere, filtered, dried at 40° C.-60° C., chromatographed, and rotary evaporated to obtain a solid product; The molar ratio of 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole and 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is 1:1.0-1.2, the molar ratio of 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine and 1 MOL / L tetrabutylammonium fluoride solution in tetrahydrofuran is 1:1.0-1.5, and the eluent during chromatography is a mixture of petroleum ether and ethyl acetate in a volume ratio of 2-5:

1.

3. The method for preparing an m-phenyl bridged alkynylpyrazole-pyridine derivative according to claim 2, characterized in that: The preparation method of the 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine is: (3-Bromophenylethynyl)trimethylsilane, 3-ethynylpyridine, tetrakistriphenylphosphine palladium, and cuprous iodide are dissolved in triethylamine and toluene, and stirred at 60°C-90°C under a nitrogen atmosphere for 12-18 hours. The mixture is filtered through celite, dried by rotation, chromatographed, and rotary evaporated to obtain 3-((3-((trimethylsilyl)ethynyl)phenyl)ethynyl)pyridine; the molar ratio of (3-bromophenylethynyl)trimethylsilane to 3-ethynylpyridine is 1:1.0-1.2; and the eluent for chromatography is pure dichloromethane.

4. The method for preparing an m-phenyl bridged alkynylpyrazole-pyridine derivative according to claim 2, characterized in that: The preparation method of the 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole is as follows: 4-Ethyl-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole, 1,3-dibromo-5-iodobenzene, bistriphenylphosphine palladium dichloride, and cuprous iodide were dissolved in triethylamine, heated under reflux at 35°C-45°C under N2 atmosphere for 8-15 hours, filtered through celite, dried at 40°C-60°C, chromatographed, and rotary evaporated to obtain 4-((3,5-dibromophenyl)ethynylene)-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole; The molar ratio of 1,3-dibromo-5-iodobenzene and 4-ethyl-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole is 1:1.0-1.2, and the eluent during chromatography is a mixture of petroleum ether and ethyl acetate in a volume ratio of 8-15:

1.

5. Use of the m-phenyl bridged alkynylpyrazole-pyridine derivative according to claim 1 in coordination chemistry and mercury ion detection, wherein the purpose of the use is not to diagnose and treat diseases.

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