Light-induced hole transfer in a hypervalent phosphorus(V) octaethylporphyrin bearing an axially linked bis(ethylenedithio) tetrathiafulvalene

A phosphorus(V) porphyrin bearing an axially linked bis(ethylenedithio) tetrathiafulvalene, dyad 1, and its radical cation phosphorus(V) porphyrin-O-CH₂-(bis(ethylenedithio)tetrathiafulvalene) ^+•, dyad 2, have been synthesized and studied as an electron hole donor-acceptor system. The absorption spectrum of dyad 1 does not show evidence for electronic coupling between the porphyrin and the bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) moieties. However, the steady-state fluorescence of the porphyrin chromophore is quantitatively quenched and its transient fluorescence lifetime is shortened compared to a reference compound in which the BEDT-TTF moiety is replaced by a methoxy group. Chemical oxidation of the BEDT-TTF moiety in dyad 1 to give dyad 2 results in recovery of the fluorescence intensity. This behavior suggests that the fluorescence quenching in dyad 1 is the result of intramolecular hole transfer from the the excited porphyrin to the BEDT-TTF moiety. The occurence of hole transfer in dyad 1 is confirmed by freeze-trapping and time-resolved electron paramagnetic resonance (EPR) measurements. The freeze-trapping EPR experiments show that steady-state irradiation of the complex leads to accumulation of its radical cation (dyad 2) while the transient EPR measurements at 5 °C show that flash irradiation of dyad 1 results in formation of a radical-ion pair with a lifetime of at least 300 ns. The triplet state of the porphyrin, which is formed by intersystem crossing and gives a strong transient EPR spectrum in the reference compound, is not observed for dyad 1. Together, the fluorescence quenching and the polarization pattern of the radical pair suggest that the hole transfer occurs from the excited singlet state of the porphyrin with high efficiency.