Evidence for a C–H⋯π type weak interaction: 1:1 complex of styrene with acetylene studied by mass selective high-resolution UV spectroscopy and ab initio calculations

Abstract

The 1:1 complex of styrene with acetylene has been studied by mass selective low- and high-resolution UV resonance-enhanced two-photon ionisation (R2PI) spectroscopy combined with genetic-algorithm-based computer-aided fit of the spectra with partial rotational resolution, and high level ab initio quantum chemistry calculations. Two stable conformeric geometries of the 1:1 complex of styrene and acetylene have been theoretically found: one with acetylene binding to styrene as a proton donor, and one with acetylene acting as a proton acceptor. From the analysis of the vibronic structure of the S₁ ← S₀ spectrum and the fit of the highly resolved spectrum of the 000 origin band of the complex it is shown that the favoured conformation is the one in which acetylene binds to the benzene ring of styrene through formation of a non-conventional hydrogen bond of C–H⋯π type with no marked change of the transition moment orientation of styrene. The styrene moiety remains planar and the acetylene molecule is tilted by a small angle of 4° relative to the C₆ symmetry axis of the benzene ring, most likely due to the reduced symmetry of the benzene ring π electrons rather than to a direct interaction with the vinyl group.