Photoisomerization of Enediynyl Linker Leads to Slipped Cofacial Hydroporphyrin Dyads with Strong Through-Bond and Through-Space Electronic Interactions

Abstract

Photoisomerization of 3,4-di(methoxycarbonyl)-enediyne linker in hydroporphyrin (chlorin or bacteriochlorin) dyads leads to thermally stable cis isomers, where macrocycles adopt a slipped cofacial mutual geometry with an edge-to-edge distance of ∼3.6 Å (determined by density functional theory (DFT) calculations). Absorption spectra exhibit a significant splitting of the long-wavelength Qy band, which indicates a strong electronic coupling with a strength of V = ∼477 cm-1 that increases to 725 cm-1 upon metalation of hydroporphyrins. Each dyad features a broad, structureless emission band, with large Stokes shift, which is indicative of excimer formation. DFT calculations for dyads show both strong through-bond electronic coupling and through-space electronic interactions, due to the overlap of π-orbitals. Overall, geometry, electronic structure, strength of electronic interactions, and optical properties of reported dyads closely resemble those observed for photosynthetic special pairs. Dyads reported here represent a novel type of photoactive arrays with various modes of electronic interactions between chromophores. Combining through-bond and through-space coupling appears to be a viable strategy to engineer novel optical and photochemical properties in organic conjugated materials.