Through-Space Spin-Spin Coupling In Acetylenic Systems. Ab Initio and DFT Calculations

We have investigated, by means of ab initio and DFT calculations, the magnitude of through-space spin-spin couplings (JCH and JHH) in CH/π bonded van der Waals dimers involving acetylene, and in a structurally related covalent compound (4ethynylphenanthrene). Within regions where the interaction is stabilizing JHH couplings are very small (< 0.1 Hz) for all complexes. In the acetylene-methane complex JCH is also very small, whereas in the acetylene-benzene complex and the acetylene dimer it shows a relatively large dependence on the tilt angle from the T-shaped arrangement, for which the smallest values are calculated, to a parallel slipped arrangement where JCH is ca. 0.5 Hz. The relative magnitude of through-space couplings in 4-ethynylphenanthrene and a tilted acetylene-benzene dimer, featuring the same internuclear arrangement as in model dimers, are compared.