Synthesis and structural and magnetic characterisation of tetranuclear Cu(ii) complexes possessing novel [Cu44-PO4)22-CO3)] butterfly cores that exhibit supramolecular isomerism

Robert P. Doyle, Paul E. Kruger, Boujemaa Moubaraki, Keith S. Murray, Mark Nieuwenhuyzen

Research output: Contribution to journalArticle

45 Scopus citations

Abstract

The reaction in water of Cu(OH)2 with 2,2′-bipyridine (bipy) and (NH4)2HPO4 (4 ∶ 4 ∶ 2) in air leads to the formation of two structurally related complexes following the fixation of CO2: ([(H2O)2Cu4(bipy)44-PO4)22-CO3)]·22.5H2O), 1, and ([(H2O)2Cu4(bipy)44-PO4)22-CO3)]·15.5H2O), 1a, as determined by single crystal X-ray diffraction. Whilst each complex contains isostructural tetranuclear Cu(ii) butterfly cores, they differ in the way they pack in the solid state: adjacent units in 1 align in parallel fashion, whereas those in 1a form H-bonded dimers in an antiparallel arrangement. 1 and 1a are therefore supramolecular isomers. 1 is encapsulated within an ‘ice-like’ 3D H-bonded water network whereas the solvent sheath about 1a forms a 2D H-bonded network. A similar product results when bipy is replaced with 1,10-phenanthroline (phen) giving ([(H2O)2Cu4(phen)44-PO4)22-CO3)]·21.5H2O), 2, which possesses an isostructural butterfly core shrouded within a 3D H-bonded water network. 2 packs in the solid-state in a similar way to 1 although, in this instance, adjacent units align in an antiparallel fashion. Both 1 and 2 may be directly synthesised in higher yields when (NH4)HCO3 is included within the reaction medium. A magnetic susceptibility study performed upon 1 reveals net weak intramolecular antiferromagnetic coupling between the Cu(ii) centres.

Original languageEnglish (US)
Pages (from-to)4230-4237
Number of pages8
JournalJournal of the Chemical Society. Dalton Transactions
Volume3
Issue number22
DOIs
StatePublished - Nov 4 2003
Externally publishedYes

Keywords

  • Bioinorganic chemistry
  • Coordination chemistry
  • Hydrogen bonding
  • Magnetic properties
  • Supramolecular chemistry

ASJC Scopus subject areas

  • Chemistry(all)

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