Synthesis and Excited-State Photodynamics of A Perylene-Monoimide-Oxochlorin Dyad. A Light-Harvesting Array

Abstract

A perylene-oxochlorin dyad has been prepared and characterized for potential use as a new light-harvesting motif. The dyad (PMI−ZnO) consists of a perylene-monoimide dye (PMI) joined at the 5-position of a zinc oxochlorin (ZnO) via a diphenylethyne linker. The dyad and its subunits have been studied in both polar and nonpolar media using static and time-resolved optical spectroscopy and electrochemical techniques. Energy flows very rapidly from both unrelaxed (vibrationally, conformationally, or electronically) and relaxed forms of the excited perylene (PMI*) to the ground-state oxochlorin with an effective time constant of ∼4 ps and an efficiency of 99% in both toluene and benzonitrile. Subsequently, there is little or no quenching of the excited oxochlorin (ZnO*) in either solvent. These findings are consistent with the expectation that all charge-separated states such as PMI - ZnO + lie energetically above both PMI* and ZnO* in both polar and nonpolar media. Furthermore, light absorption by the perylene and oxochlorin occurs in complementary regions, giving broad spectral coverage. Thus, the new perylene-oxochlorin dyad is an excellent light-harvesting unit that can be incorporated into more elaborate architectures for use in solar-energy and molecular-photonics applications.