All inorganic coordination polymers have been made possible with the m-carboranylphosphinate ligand

Abstract

New examples of 1D coordination polymers (CPs) and complexes containing the purely inorganic carboranylphosphinate ligand [1-OPH(O)-1,7-closo-C₂B₁₀H₁₁]⁻ are reported. The reaction of Na[1-OPH(O)-1,7-closo-C₂B₁₀H₁₁] salt with MCl₂ (M = Mn, Co, Ni, Cu, Zn and Cd) in MeOH or EtOH leads to compounds 1–8. All compounds have been exhaustively characterized by analytical and spectroscopic techniques. X-ray analysis and spectroscopy characterization revealed the differences between the isolated compounds: 1D polymeric chains (CPs) with carboranylphosphinate ligand bridges have been obtained with Mn^II, Cd^II or Zn^II centres, whereas compounds with low nuclearity have been isolated with Cu^II, Co^II and Ni^II. No polymeric structures were obtained in the Co^II and Ni^II complexes due to the higher affinity of these metals for water than that for the m-carboranylphosphinate and accordingly, these complexes generate supramolecular hydrophobic/hydrophilic structures. The reactivity of manganese polymer 1 with water leads to the breakage of the polymer with the formation of a new mononuclear compound 2, and that in methanol leads back to the initial polymer 1. However, the reactivity of polymer 1 with 2,2′-bpy maintains the core present in the initial polymer, leading to the CP 3, which in methanol/water medium produces species of lower nuclearity. The magnetic properties of the compounds studied show weak antiferromagnetic coupling.