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DOI: 10.1039/A700107J (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 2131-2138

Pentanuclear copper(II) complexes with the novel 6-(phenylethynyl)-2-pyridonate ligand: synthesis, structures and magnetic properties

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Allan A. Doyle, Simon Parsons, Gregory A. Solan and Richard E. P. Winpenny

Abstract

Three pentanuclear copper(II) complexes, [Cu5(OMe)2(CF3CO2)(pehp) 6(Cl)] 1, [Cu5(OMe)2(CF3CO2)(pehp) 6(NO3)] 2 and [Cu5(OH)(CF3CO2)3(pehp) 6] 3, have been prepared via the solid-state reaction of hydrated copper(II) nitrate with the sodium salt of the novel ligand, 6-(phenylethynyl)-2-pyridone (Hpehp) in the presence of sodium trifluoroacetate. Crystal structural analysis at 220 K of 1–3 reveals capped-butterfly arrangements of the five copper atoms with the two shortest Cu · · ·[hair space] [hair space]Cu vectors in 1 and 2 [3.024(6)–3.050(3) Å] occurring between the caps and the wingtips while in 3 the wingtip–cap distances are more asymmetric with one short [3.042(7) Å] and one long [3.638(7) Å] Cu · · ·[hair space] [hair space]Cu vector. Mass spectroscopic studies of 1–3 show fragmentation patterns consistent with the observed structures, while magnetic studies of the complexes indicate antiferromagnetic exchange coupling within the Cu5 cores and S = ½ ground states for all compounds. The trifluoroacetate adduct of Hpehp, Hpehp·0.5CF3CO2H was synthesised in three steps from 2-bromo-6-benzyloxypyridine via 2-benzyloxy-6-(phenylethynyl)pyridine and the single crystal X-ray structure of Hpehp was also determined.

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