Efficient Electron Transfer Driven by Excited-State Structural Relaxation in Corrole-Perylenedimiide Dyad.

A sterically encumbered -AB-corrole possessing a perylenediimide (PDI) scaffold in close proximity to the macrocycle has been synthesized via a straightforward route. Electronic communication as probed via steady-state absorption or cyclic voltammetry is weak in the ground state, in spite of the corrole ring and PDI being bridged by an -phenylene unit. The TDDFT excited-state geometry optimization suggests after excitation the interchromophoric distance is markedly reduced, thus enhancing the through-space electronic coupling between the corrole and the PDI.