Flexible Molecular Precursors for Selective Decomposition to Nickel Sulfide or Nickel Phosphide for Water Splitting and Supercapacitance.

Herein, the synthesis of three nickel(II) dithiophosphonate complexes of the type [Ni{S P(OR)(4-C H OMe)} ] [R=H (1), C H (2)] and [Ni{S P(OR)(4-C H OEt} ] [R=(C H ) CH (3)] is described; their structures were confirmed by single-crystal X-ray studies. These complexes were subjected to surfactant/solvent reactions at 300 °C for one hour as flexible molecular precursors to prepare either nickel sulfide or nickel phosphide particles. The decomposition of complex 2 in tri-octylphosphine oxide/1-octadecene (TOPO/ODE), TOPO/tri-n-octylphosphine (TOP), hexadecylamine (HDA)/TOP, and HDA/ODE yielded hexagonal NiS, Ni P, Ni P , and rhombohedral NiS, respectively.