Synthesis and Self-Aggregation of π-Expanded Chlorophyll Derivatives to Construct Light-Harvesting Antenna Models

Chlorosomes are one of the elegant light-harvesting antenna systems in anoxygenic photosynthetic bacteria, whose core is constructed from J-type self-aggregation of bacteriochlorophyll- c, bacteriochlorophyll- d, bacteriochlorophyll- e, and bacteriochlorophyll- f molecules without the influence of polypeptides. Chlorosomal supramolecular models were built up using synthetic porphyrin-type bacteriochlorophyll- d analogues with a methoxycarbonylethenyl, formyl, vinyl, or ethyl group at the 8-position. Their chlorosomal self-aggregates in an aqueous micelle solution showed relatively intense absorption bands around 500-600 nm where antennas of natural oxygenic phototrophs, as well as green sulfur bacteria possessing bacteriochlorophylls- c/ d, absorb light less efficiently; this observation is called the "green gap". Furthermore, the functional chlorosomal models were constructed by simple addition of a small amount of an energy acceptor model bearing a bacteriochlorin moiety to the pigment self-assemblies in an aqueous micelle. The resulting excited energy donor-acceptor supramolecules played the roles of chlorosomal light-harvesting and energy-transfer antenna systems and were efficient at light absorption in the "green gap" region.