Hydrothermal chemistry of oxomolybdenum-1,4-carboxyphenylphosphonates in the presence of M(II)-organonitrogen building blocks (M(II) = Co, Ni, and Cu).

Paul Deburgomaster, Amanda Aldous, Hongxue Liu, Charles J. O'Connor, Jon Zubieta

Research output: Contribution to journalArticle

35 Scopus citations

Abstract

Hydrothermal methods were used to prepare a series of materials of the M(II)-L'/MoxOy/H2O3PC 6H4CO2H family, where M(II) = Co, Ni, or Cu and L' = 2,2'-bipyridine (bpy), o-phenanthroline (phen), or 2,2':6,2"- terpyridine (terpy). The common {Mo5O15(O 3PR)2}4- cluster provided a building block for the one-dimensional (1D) structure of [{Cu(bpy)(H2O)} 3{O2CC6H4PO3} 2Mo5O15]•4.5H2O (1•4.5H2O). While the pentamolybdate cluster was observed for [Co(terpy)2][Mo5O14(OH){HO2CC 6H4PO3}2]•5.25H2O (5•5.25H2O) and [Ni(phen)2(H2O) 2][Ni(phen)2Mo5O15{HO 2CC6H4PO3}2]•2H 2O (6•2H2O), the clusters are present as discrete molecular anions. In contrast, the 1D structure of [Cu(bpy){O3PC 6H4CO2H}Mo2O6] (2) exhibits a {Mo2O6}n2n+ chain, decorated with phosphonate and {Cu(phen)}2+ groups. The three-dimensional (3D) structure of [{Cu(phen)}2Mo2O5{O3PC 6H4CO2}2]•H2O (3•H2O) is constructed from {Mo2O5} 2+ binuclear units, linked into chains through bridging {Cu(phen)}2+ groups; the chains are in turn connected through the dipodal carboxyphenylphosphonate ligands to produce the overall 3D connectivity. Fluoride incorporation in [Cu(bpy){O3PC6H 4CO2}MoO2F] (4) results in mononuclear {MoO5F} octahedra linked through {Cu(bpy)}2+ units and the organophosphonate ligand into a chain. The molecular structure of the second polyoxofluoromolybdate species [Co(bpy)3]2[Mo 12F4O34(H2O)4{O 3PC6H4CO2H}2] •4H2O (7•4H2O) consists of discrete {Co(bpy)3}2+ cations and [Mo12F 4O34(H2O)4{O3PC 6H4CO2H}2]4- anionic clusters. The unique dodecamolybdate unit of 7 consists of two {Mo 6F2O17(H2O)2(O 3PR)2}2- subunits fused through two bridging oxo-groups.

Original languageEnglish (US)
Pages (from-to)2209-2218
Number of pages10
JournalCrystal Growth and Design
Volume10
Issue number5
DOIs
StatePublished - May 5 2010

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

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