Solid state coordination chemistry: Structural consequences of varying diphosphonate tether length and fluoride incorporation in he copper-bisterpy/oxomolybdenum/organodiphosphonate system (bisterpy = 2,2′:4′,4″:2″,2′″-quarterpyridyl-60, 600-di-2-pyridine)

Stephanie Jones, José M. Vargas, Steven Pellizzeri, Charles J. O'Connor, Jon A Zubieta

Research output: Contribution to journalArticle

12 Scopus citations

Abstract

The hydrothermal reactions of Cu(C2H3O 2)2·H2O, MoO3, 2,2':4',4″:2″,2'″-quarterpyridyl-6',6″-di-2-pyridine (bisterpy), and organodiphosphonate ligands of varying carbon chain length in the presence of HF yield a series of novel organic-inorganic hybrid materials of the oxomolybdenum-organophosphonate family. All compounds of the study were characterized by elemental analysis, IR spectroscopy, TGA, magnetic susceptibility and single crystal X-ray diffraction. A common feature within the architectures of both the three-dimensional structure of [{Cu 2(bisterpy)(H2O)}Mo5O15{O 3P(CH2)4PO3}]·4.5H 2O (1) and the one-dimensional structure of [{Cu 2(bisterpy)(H2O)2}Mo5O 15{O3P(CH2)5PO3}] (2) is the presence of {Mo5O15(O3PR)2} 4- clusters as building blocks. In the one-dimensional [{Cu 2(bisterpy)(H2O)2}Mo2F 6O4{- HO3P(CH2)4PO 3H}] (6), {Cu2(bisterpy)}Mo2F4O 4{HO3P(CH2)5PO3H} 2]·2H2O (7.2H2O), [{Cu 2(bisterpy)(H2-O)2}Mo4F 8O8{O3P(CH2)6PO 3}]·H2O (8·H2O) and [{Cu 2(bisterpy)(H2O)2}Mo4F 8O8{O3P(CH2)9PO 3}] (9), the two-dimensional [{Cu2(bisterpy)(OH)}Mo 2F3O4{O3P(CH2)PO 3}]·11H2O (3·11H2O) and [{Cu 2(bisterpy)(H2O)2}Mo4F 4O10{O3P(CH2)2PO 3}] (4), and the three-dimensional [{Cu2(bisterpy)}Mo 4F6O9{O3P(CH2) 3PO3}] (5), the pentamolybdate core has not been formed due to the incorporation of fluoride ions; rather a variety of {Mo xFyOz} units link the copper-bisterpy units. All structures contain the secondary metal-ligand {Cu2(bisterpy) (H2O)x} binuclear unit. The materials of this study demonstrate the wide structural variety available to this family of compounds by modifying both the carbon chain length of the organodiphosphonate ligand and by incorporation of fluoride within the structure.

Original languageEnglish (US)
Pages (from-to)44-57
Number of pages14
JournalInorganica Chimica Acta
Volume395
DOIs
StatePublished - Jan 30 2013

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Keywords

  • Bottom-up synthesis
  • frameworks
  • Hydrothermal synthesis
  • Metal oxyfluorides
  • Molybdophosphonate building units
  • Polyoxometalate based metal organic

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

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