Polymeric and cyclic manganese phosphates and phosphinates: Synthesis, spectral characterization and solid-state structures

•The choice of metal precursor in determining the aggregation and structure of Mn(II) phosph(in)ates is demonstrated.•The influence of perchlorate on the nuclearity of the resultant metal phosph(in)ates is established.•Replacement of acetate from [Mn(OAc)(bpy)2](ClO4)(H2O) by a phosphate (L) leads to dimeric [Mn(L)(bpy)2]2(ClO4)2.•Replacement of acetate by phenyl phosphinate leads to the formation of [Mn(ppi)2(L)]n polymers.

Polymeric manganese phosphinates [Mn(ppi)2(bpy)]n (1) and [Mn(ppi)2(phen)]n (2) have been obtained by treating manganese acetate with phenylphosphinic acid (ppi-H) in the presence of either 2,2′-bpy or 1,10-phen, respectively. The reaction of preformed precursor [Mn(OAc)(bpy)2](ClO4)(H2O) with phosphinic acids or phosphate diesters yield [Mn(L)(bpy)2]2(ClO4)2 (where L-H = dtbp-H = di-tert-butyl hydrogen phosphate (3), dpp-H = diphenyl hydrogen phosphate (4), dppi-H = diphenyl phosphinic acid (5), and ppi-H = phenyl phosphinic acid (6)), which are dimeric compounds. Polymers 1–2 and dinuclear cyclic compounds 3–6 have been extensively characterized by analytical and spectroscopic methods and also in each case by a single crystal X-ray diffraction study.

Graphical abstractPolymeric manganese phosphinates [Mn(ppi)2(bpy)]n (1) and [Mn(ppi)2(phen)]n (2) have been obtained by treating manganese acetate with phenylphosphinic acid (ppi-H) in the presence of either 2,2’-bpy or 1,10-phen, respectively. The reaction of preformed precursor [Mn(OAc)(bpy)2](ClO4)(H2O) with phosphinic acids or phosphate diesters yield [Mn(L)(bpy)2]2(ClO4)2 (where L–H = dtbp-H = di-tert-butyl hydrogen phosphate (3), dpp-H = diphenyl hydrogen phosphate (4), dppi-H = diphenyl phosphinic acid (5), and ppi-H = phenyl phosphinic acid (6)), which are dimeric compounds. Polymers 1–2 and dinuclear cyclic compounds 3–6 have been extensively characterized by analytical and spectroscopic methods and also in each case by a single crystal X-ray diffraction study.Figure optionsDownload full-size imageDownload as PowerPoint slide