Probing photoinduced electron transfer events in phenylferrocene-corrole dyad.

Abstract

Herein, we investigated PhFC (10-phenylferrocenyl-5,15-diphenyl corrole), a corrole-based donor-acceptor (D-A) dyad, to understand the energy/electron transfer reaction dynamics. Phenylferrocene acts as the donor moiety when attached to the meso position of the corrole ring in the PhFC D-A system. The photophysical properties of the PhFC dyad and its parent molecule, TPC (5,10,15-triphenyl corrole), were studied by UV-vis spectroscopy, steady state fluorescence spectroscopy, TCSPC and optical microscopy techniques. A slight red shift and broadening of both the Q-band and Soret bands are observed in the absorption spectra of the PhFC dyad in comparison to TPC, representing the weak electronic interaction between the phenylferrocene moiety and corrole ring. The fluorescence emission spectrum of the PhFC dyad is significantly quenched (>80%) in comparison to TPC, attributed to the photoinduced electron transfer (PET) from phenylferrocene to the corrole ring. We observed that the electron transfer rate in the PhFC system is solvent dependent. Our theoretical investigation supported the experimental findings on the electron transfer mechanism. The HOMO and LUMO arrangements of these PhFC dyads demonstrate the electron density distribution and the ability of the donor moieties to transfer electrons to the corrole moiety. Fluorescence lifetime imaging microscopy (FLIM) was used to image the homogeneous lifetime distribution of the PhFC dyad and TPC.