Evidence of C-F···H-C Attractive Interaction: Enforced Coplanarity of a Tetrafluorophenylene-Ethynylene-Linked Porphyrin Dimer.

Abstract

The formation of C-F···H-C "hydrogen bonds" has been a controversial subject because, in principle, fluorine is hardly an acceptor for less acidic protons contrasting to the C-F···H-O and C-F···H-N hydrogen bonds. Nevertheless, the interaction is emerging as a powerful implement for confining the torsional rotation in the design of fully coplanar π-conjugated polymers. Heretofore, no evidence of the C-F···H-C interaction has been observed in solutions. We herein disclose comprehensive evidence that the C-F···H-C interaction produces an attractive force. A 19F-1H heteronuclear Overhauser effect experiment elucidated the close proximity of the F and H atoms in the doubly edge-facing C-F···H-C interactions of a meso-tetrafluorophenylene-ethynylene-conjugated porphyrin dimer (1). Extensive electronic and photophysical property investigations confirmed that all the aromatic units were torsionally restricted by the C-F···H-C interactions. Moreover, the enforced coplanarity invoked a markedly high π-staking propensity. Thus, we have firmly established the formation of a C-F···H-C interaction that produces a hydrogen-bond-like attractive force in solution.