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The first hexanuclear copper(I) carboxylate: X-ray crystal structure and reactivity in solution and gas-phase
Yulia Sevryugina1, Andrey Yu Rogachev, Marina A Petrukhina
1Department of Chemistry, University at Albany, 1400 Washington Avenue, Albany, New York 12222, USA.
Abstract:
The carboxylate ligand-exchange reaction of copper(I) trifluoroacetate by 3,5-difluorobenzoate yielded a new product, [Cu(O2C(3,5-F)2C6H3)] (1). Single crystals of 1 suitable for X-ray structural characterization were obtained by sublimation-deposition procedures at 230 degrees C. An X-ray diffraction study revealed a remarkable planar hexanuclear copper(I) core supported by bridging carboxylates, the first such structural type among other known copper(I) carboxylates. The Cu...Cu distances within the core range from 2.7064(8) to 2.8259(8) A and fall into the category of cuprophillic interactions. The hexacopper unit remains intact upon gas-phase deposition with a planar polyarene, coronene (C24H12), to give [Cu6(O2C(3,5-F)2C6H3)6](C24H12) (2). Density functional theory calculations suggest the latter compound to be a cocrystallization product having electrostatic interactions between the hexacopper complex and coronene. However, cocrystallization affects the photophysical properties of 2. While copper(I) 3,5-difluorobenzoate (1) exhibits photoluminescence at ca. 554 nm (lambda(ex) = 350 nm) in the solid state, compound 2 is nonluminescent at room temperature in the visible region. Gas-phase and solution reactions of 1 with alkyne ligands, diphenylacetylene (C14H10) and 1,4-bis(p-tolylethynyl)benzene (C24H18), result in the rupture of the [Cu6] core to afford dinuclear organometallic copper(I) complexes. The latter have a dimetal core cis-bridged by two carboxylate groups with acetylene ligands eta(2)-coordinated to each copper(I) center.
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