Larger pores and higher Tc: {[Ni(cyclam)]3[W(CN)8]2·solv}n – a new member of the largest family of pseudo-polymorphic isomers among octacyanometallate-based assemblies

摘要: A new crystalline pseudo-polymorphic form of the 2D microporous honeycomb-like magnetic network {[Ni(cyclam)]3[W(CN)8]2·solv}n was obtained from reaction between methanol-soluble {Ni[Ni(MeOH)3]8[W(CN)8]6} clusters and [Ni(cyclam)]2+ complex in an acetonitrile-rich solvent mixture. In comparison to three earlier characterised pseudo-polymorphs, which all crystallised triclinic space group P, shows higher symmetry C2/m, greater porosity ca. 40% accessible volume, highest ordering temperature 12 K. It undergoes irreversible single-crystal-to-single-crystal transformation hexadecahydrate that is stable air at ambient temperature. synthetic pathway leading directly methanol solvate same network, previously by sorption MeOH into anhydrous form, also reported.