Cation−π and CH−π Interactions in the Coordination and Solvation of Cu+(acetylene)n Complexes

Copper-acetylene cation complexes of the form Cu(C2H2)n+ (n = 1–8) are produced by laser ablation in a supersonic expansion of acetylene/argon. The ions are mass selected and studied via infrared laser photodissociation spectroscopy in the C–H stretching region (3000–3500 cm–1). The structure and bonding of these complexes are investigated through the number of infrared active bands, their relative intensities and their frequency positions. Density functional theory calculations are carried out in support of the experimental data. The combined data show that cation−π complexes are formed for the n = 1–3 species, resulting in red-shifted C–H stretches on the acetylene ligands. The coordination of the copper cation is completed with three acetylene ligands, forming a “propeller” structure with D3 symmetry. Surprisingly, complexes with even greater numbers of acetylenes than this (4–6) have distinctive infrared band patterns quite different from those of the smaller complexes. Experiment combined with theory...