Meso-Biphenyl-Linked, Near- and Far-Infrared Emitting, Chlorin and Bacteriochlorin Dimers: Synthesis, Excitation Transfer, and Singlet Oxygen Production

A series of meso-biphenyl linked chlorin and bacteriochlorin dimers, derived from naturally occurring chlorophyll (Chl-a) and bacteriochlorophyll (BChl-a) were synthesized in 32 % to 44 % yields and characterized, as photosynthetic antenna mimics, and a new class of singlet oxygen producing agents. The dimers are characterized by absorption, fluorescence, electrochemical, spectroelectrochemical and computational methods to evaluate their physico-chemical properties, and to identify ground and excited state interactions. Evidence of excited energy exchange among the chromophores in the dimer is derived from femtosecond transient absorption spectral studies. Rate constants for excitation hopping were in the order of 10¹¹ s⁻¹, indicating occurrence of efficient processes. Nanosecond transient absorption studies confirmed relaxation of the singlet excited chlorin and bacteriochlorin dimers to their corresponding triplet states (³Chl* and ³Bchl*). As predicted by the established energy level diagrams, both ³Chl* and ³Bchl* are shown to be capable of producing singlet oxygen with appreciable quantum yields (ϕ_SO∼0.3).