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.