Study Of Tetracyanometallate-based Coordination Polymersconstructed By Bidentate Ligands With Nitrogen-atom

Tetracyanometallate-based coordination polymers have important values of research in the field of coordination chemistry, due to their interesting topological structures and excellent properties. In this paper, twenty-two new coordination polymers were synthesized by using [M’(CN)4]2-(M’ = Ni, Pd, Pt) building blocks to react with transition metal ions and bidentate ligands with nitrogen-atom. These materials have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, infrared and thermal-gravity analysis. In addition, gas adsorption properties of some coordination polymers have been also investigated.Four coordination polymers Cd(py)2][Ni(CN)4](1), [Cd(2-chloropyrazine)(H2O)]-[Ni(CN)4](2), [Cd(2-chloropyrazine)(H2O)][Pt(CN)4](3), and [Cd(2-chloropyrazine)2]-[Pd(CN)4](4) have been prepared by the self-assembly of [M’(CN)4]2-(M’ = Ni, Pd, Pt), Cd2+ and py/2-chloropyrazine. Single-crystal X-ray diffraction analysis showed that 1 belong to orthorhombic Pmna space group, and has a 2D wavy plane structure; 2 belong to orthorhombic Pnma space group and has a 2D wavy plane structure; 3 belong to orthorhombic P212121 space group and has a 3D porous structure; 4 belong to monoclinic P21/c space group and has a 2D wavy plane structure.Three coordination polymers [Cd(bpy)][Ni(CN)4](5), [Mn(bpac)2(H2O)2][Pt(CN)4](6), and [Mn(bpac)2(H2O)2][Pd(CN)4](7) have been prepared by the self-assembly of [M’(CN)4]2-(M’ = Ni, Pd, Pt), Cd2+, Mn2+ and dpe/azpy. Single-crystal X-ray diffraction analysis showed that 5 belong to orthorhombic Pmma space group and has a 3D Hofmann-like framework; 6 and 7 are isostructural and belong to triclinic P1 space group, they have a 1D straight chains structure. Among them, 5 has much lower uptakes for nitrogen and hydrogen.Six coordination polymers [Cd(dpe)][Ni(CN)4](8), [Cd(dpe)2][Cd(dpe)(H2O)2]-[Pt(CN)4]2(9), [Mn(azpy)][Ni(CN)4]·C2H6O·0.5H2O(10), [Cd(azpy)][Ni(CN)4]·C2H6O·0.5-H2O(11), [Cd(azpy)][Pt(CN)4](12), and [Cd(azpy)][Pd(CN)4](13) have been prepared by the self-assembly of [M’(CN)4]2-(M’ = Ni, Pd, Pt), Cd2+, Mn2+and dpe/azpy. Single-crystal X-ray diffraction analysis showed that 8 belong to orthorhombic Pbam space group and has 3D Hofmann-like framework; 9 belong to monoclinic C2/c space group and has 3D framework; 10 and 11 are isostructural and belong to orthorhombic Pbam space group, they have a 3D Hofmann-like framework; 12 and 13 are isostructural and belong to orthorhombic Pmma space group, they have a 3D Hofmann-like framework. Among them, 8 has much lower uptakes for hydrogen; 11 has low uptakes for hydrogen, nitrogen and caron dioxide.Nine coordination polymers [Cd(dps)][Ni(CN)4](14), [Cd(dps)][Pd(CN)4](15),[Cd(H2O)2][Cd(dps)2][Pt(CN)4]2(16), [Cd(dps)][Pt(CN)4](17), [Cd(dps)][Pd(CN)4](18), [Mn(dps)2][Ni(CN)4]·H2O(19), [Cd(dps)2][Ni(CN)4]·H2O(20), [Zn(dps)2][Ni(CN)4](21), and [Fe(dps)2][Ni(CN)4]·H2O(22) have been prepared by the self-assembly of [M’(CN)4]2-(M’ = Ni, Pd, Pt), Cd2+, Mn2+, Zn2+, Fe2+ and dps. Single-crystal X-ray diffraction analysis showed that 14 and 15 are isostructural and belong to triclinic P-1 space group, they have a 3D Hofmann-like framework; 16 belong to triclinic P-1 space group and has a 2D wavy plane structure; 17 and 18 are isostructural and belong to monoclinic C2/c space group, they have a 3D framework; 19 and 20 are isostructural and belong to orthorhombic P212121 space group, they have a 2D wavy plane structure; 21 belong to monoclinic P2/n space group and has a 2D wavy plane structure; 22 belong to monoclinic C2/c space group and has a 2D plane structure. 14 and 17 have high thermal stabilities. Among them, 14 has a much lower uptake for nitrogen with 0.2889 mmol/g.