含S芳香羧酸配位聚合物的构筑、结构及其性能研究
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摘要
金属-羧酸配位聚合物具有丰富多彩的拓扑结构,在光、电、磁、催化等诸多领域有着广泛的应用前景。本文依据晶体工程学原理,选择巯基苯甲酸为初始配体与金属离子反应,采用水热和溶液法成功地合成了12个具有一维,二维和三维结构的配位聚合物：
Mn(p-HTAB)2(bpp)2(H2O)2 (1)
[Ni(p-TAB)(4,4'-bipy)(H2O)3]-H2O (2)
[Co(p-HTAB)2(4,4'-bipy)2(H2O)2]·H2O (3)
[Zn(p-HTAB)2(4,4'-bipy)2(H2O)2]·H2O (4)
[Ni(p-HTAB)2(4,4'-bipy)2(H2O)2]·H2O (5)
Cd2(m-TAB)2(4,4'-bipy)3/2(H2O)2 (6)
Cd(m-TAB)(phen) (7)
[Cd(3,3'-DTBB)(phen)]·H2O (8)
Co(3,3'-DTBB)4(4,4'-bipy)4 (9)
Pb(p-SB)(2,2'-bipy)(H2O) (10)
[Ag(NO3)(4,4'-bipy)][Ag(o-HSB)(4,4'-bipy)]·2H2O (11)
[Ag(H2O)(4,4'-bipy)][Ag(o-SB)(4,4'-bipy)]·2H2O (12)
利用元素分析、红外光谱、热重分析对这些配位聚合物进行了初步表征,并用X-射线单晶衍射测定了这些配位聚合物的晶体结构,研究了特定配合物的荧光、电化学性质和生物活性。初步总结了含硫芳香羧酸配位聚合物的组装方法及其空间结构调控规律,探讨了部分配合物结构与性能的关系和规律。
Metal-organic coordination polymers based on carboxylate ligands have diverse topology structures and potential applications in the areas of optical, electronic, magnetic and catalytic properties. In this manuscript, we chose thiosalicylic acid as original ligand coordinating with metal ions and synthesized a series of 1D,2D and 3D coordination polymers by hydrothermal synthetic and solution methods according to crystal engineering theory. They are shown as following:
Mn(p-HTAB)2(bpp)2(H2O)2 (1)
[Ni(p-TAB)(4,4'-bipy)(H2O)3]·H2O (2)
[Co(p-HTAB)2(4,4'-bipy)2(H2O)2]·H2O (3)
[Zn(p-HTAB)2(4,4'-bipy)2(H2O)2]·H2O (4)
[Ni(p-HTAB)2(4,4'-bipy)2(H2O)2]·H2O (5)
Cd2(m-TAB)2(4,4'-bipy)3/2(H2O)2 (6)
Cd(m-TAB)(phen) (7)
[Cd(3,3'-DTBB)(phen)]·H2O (8)
Co(3,3'-DTBB)4(4,4'-bipy)4 (9)
Pb(p-SB)(2,2'-bipy)(H2O) (10)
[Ag(NO3)(4,4'-bipy)][Ag(o-HSB)(4,4'-bipy)]·2H2O (11)
[Ag(H2O)(4,4'-bipy)][Ag(o-SB)(4,4'-bipy)]·2H2O (12)
Polymers were characterized by IR, elementary analysis, thermo-gravimetric and X-ray single crystal diffraction. Luminescence, electrochemical properties and biological activities were studied for some polymers. It was also investigated how to control the assembly of coordination polymers with desired properties, moreover, the relation between structure and property was discussed.
Mn(p-HTAB)2(bpp)2(H2O)2 (1)
[Ni(p-TAB)(4,4'-bipy)(H2O)3]-H2O (2)
[Co(p-HTAB)2(4,4'-bipy)2(H2O)2]·H2O (3)
[Zn(p-HTAB)2(4,4'-bipy)2(H2O)2]·H2O (4)
[Ni(p-HTAB)2(4,4'-bipy)2(H2O)2]·H2O (5)
Cd2(m-TAB)2(4,4'-bipy)3/2(H2O)2 (6)
Cd(m-TAB)(phen) (7)
[Cd(3,3'-DTBB)(phen)]·H2O (8)
Co(3,3'-DTBB)4(4,4'-bipy)4 (9)
Pb(p-SB)(2,2'-bipy)(H2O) (10)
[Ag(NO3)(4,4'-bipy)][Ag(o-HSB)(4,4'-bipy)]·2H2O (11)
[Ag(H2O)(4,4'-bipy)][Ag(o-SB)(4,4'-bipy)]·2H2O (12)
利用元素分析、红外光谱、热重分析对这些配位聚合物进行了初步表征,并用X-射线单晶衍射测定了这些配位聚合物的晶体结构,研究了特定配合物的荧光、电化学性质和生物活性。初步总结了含硫芳香羧酸配位聚合物的组装方法及其空间结构调控规律,探讨了部分配合物结构与性能的关系和规律。
Metal-organic coordination polymers based on carboxylate ligands have diverse topology structures and potential applications in the areas of optical, electronic, magnetic and catalytic properties. In this manuscript, we chose thiosalicylic acid as original ligand coordinating with metal ions and synthesized a series of 1D,2D and 3D coordination polymers by hydrothermal synthetic and solution methods according to crystal engineering theory. They are shown as following:
Mn(p-HTAB)2(bpp)2(H2O)2 (1)
[Ni(p-TAB)(4,4'-bipy)(H2O)3]·H2O (2)
[Co(p-HTAB)2(4,4'-bipy)2(H2O)2]·H2O (3)
[Zn(p-HTAB)2(4,4'-bipy)2(H2O)2]·H2O (4)
[Ni(p-HTAB)2(4,4'-bipy)2(H2O)2]·H2O (5)
Cd2(m-TAB)2(4,4'-bipy)3/2(H2O)2 (6)
Cd(m-TAB)(phen) (7)
[Cd(3,3'-DTBB)(phen)]·H2O (8)
Co(3,3'-DTBB)4(4,4'-bipy)4 (9)
Pb(p-SB)(2,2'-bipy)(H2O) (10)
[Ag(NO3)(4,4'-bipy)][Ag(o-HSB)(4,4'-bipy)]·2H2O (11)
[Ag(H2O)(4,4'-bipy)][Ag(o-SB)(4,4'-bipy)]·2H2O (12)
Polymers were characterized by IR, elementary analysis, thermo-gravimetric and X-ray single crystal diffraction. Luminescence, electrochemical properties and biological activities were studied for some polymers. It was also investigated how to control the assembly of coordination polymers with desired properties, moreover, the relation between structure and property was discussed.
引文
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