Spectral, electrochemical, and photophysical studies of a magnesium porphyrin–fullerene dyad

Abstract

A covalently linked magnesium porphyrin–fullerene (MgPo–C₆₀) dyad was synthesized and its spectral, electrochemical, molecular orbital, and photophysical properties were investigated and the results were compared to the earlier reported zinc porphyrin–fullerene (ZnPo–C₆₀) dyad. The ab initio B3LYP/3-21G(*) computed geometry and electronic structure of the dyad predicted that the HOMO and LUMO are mainly localized on the MgP and C₆₀ units, respectively. In o-dichlorobenzene containing 0.1 M (n-Bu)₄NClO₄, the synthesized dyad exhibited six one-electron reversible redox reactions within the potential window of the solvent. The oxidation and reduction potentials of the MgP and C₆₀ units indicate stabilization of the charge-separated state. The emission, monitored by both steady-state and time-resolved techniques, revealed efficient quenching of the singlet excited state of the MgP and C₆₀ units. The quenching pathway of the singlet excited MgP moiety involved energy transfer to the appended C₆₀ moiety, generating the singlet excited C₆₀ moiety, from which subsequent charge-separation occurred. The charge recombination rates, k_CR, evaluated from nanosecond transient absorption studies, were found to be 2–3 orders of magnitude smaller than the charge separation rate, k_CS. In o-dichlorobenzene, the lifetime of the radical ion-pair, MgPo˙⁺–C₆₀˙⁻, was found to be 520 ns which is longer than that of ZnPo˙⁺–C₆₀˙⁻ indicating better charge stabilization in MgPo–C₆₀. Additional prolongation of the lifetime of MgPo˙⁺–C₆₀˙⁻ was achieved by coordinating nitrogenous axial ligands. The solvent effect in controlling the rates of forward and reverse electron transfer is also investigated.