Network topologies and properties of cyanoplatinate coordination polymers

This work is a contribution to the rich literature on cyanoplatinate chemistry, with a focus on the synthesis and materials properties of coordination polymers that incorporate [Pt(CN)4]2– and [PtX2(CN)4]2– (X = Cl, Br) as linkers. Furthermore, fundamental Pt2+ chemistry is explored in the synthesis of new linkers incorporating the ligand iso-maleonitriledithiolate (i-mnt) for use in chemical sensors and negative thermal expansion materials. Combination of M2+ with [PtX2(CN)4]2– (X = Cl, Br) results in the formation of solvent-templated coordination polymers with networks of varying hydration, M(H2O)n[PtX2(CN)4]·m/3H2O (n = 0 to 2; m = 0 to 8). The structures of the coordination polymers are described; characterization methods include IR, Raman, TGA, EA, and variable temperature XRD. A comparative study between the thermal expansion properties of Cu(H2O)2[PtX2(CN)4] and Cu[PtX2(CN)4] highlights the impact of solvent on the thermal expansion of these materials. The ability of Cu(H2O)2[PtX2(CN)4] (X = Cl, Br) to act as vapochromic sensors and their vapour adducts Cu(L)2[PtX2(CN)4] (L = DMSO, DMF, Pyridine; X = Cl, Br) are reported. Some simple amine-containing compounds were also prepared, and a structural analysis carried out on the pyrazine-containing M(H2O)2[PtBr2(CN)4]·2pyz (M = Co2+, Zn2+, and Cd2+) and Cu(pyz)[PtBr2(CN)4] compounds. The structures, optical, and thermal properties of new [Pt(CN)4]2– coordination polymers prepared by combination with Pb2+, Cd2+, and Mn2+ are reported. The interplay between the Pt4+ halogenated and Pt2+ non-halogenated materials for X2 (X = Cl, Br) sensing is also studied. Attempts to isolate [Pt(i-mnt)2]2– and combination with d10 M2+ for chemical sensors, and conditions for oxidation to [Pt(i-mnt)3]2– are discussed. A series of new asymmetric i-mnt-containing Pt complexes have also been prepared. Metal organic frameworks formed from the combination of the Pd2+ analogues and M2+, M(H2O)4[Pd(i-mnt)2] (M = Mn2+, Co2+, Zn2+), have also been prepared and fully characterized.