Addressing Through-H Magnetic Interactions: A Comprehensive ab Initio Analysis of This Efficient Coupler.

The exchange coupling in a structuraly characterized CuII2 complex is analyzed to highlight the role of H bonds in the generation of efficient magnetic interactions. The interest for complementary insights which are not accessible through DFT calculations (Desplanches, C. et al. J. Am. Chem. Soc. 2002, 124, 5197) has driven this state-of-the-art ab initio inspection. The wave function expansion based upon localized orbitals allows us to selectively turn on specific mechanisms and quantitatively evaluate their roles in the exchange interactions. Our singlet−triplet splitting calculations demonstrate the enhancement of the magnetic coupling through a concerted oxygen-to-metal charge transfer and electronic redistribution within the OH bond of the OH···O magnetic linker. This mechanism accounts for ∼35% of the total experimentally measured singlet−triplet energy difference. This analysis strongly suggests that H bonds might be particularly useful not only in the establishment of intermolecular contacts but a...