Hierarchal Light-Harvesting Aggregates and Their Potential for Solar Energy Applications.

The tunable optical properties of self-assembled chromophores are exploited by photosynthetic organisms to optimize their ability to harvest a broad range of the solar spectrum. Similarly, the efficiency of solar photovoltaic and photoelectrochemical devices depends strongly on the coincidence of the absorption spectrum of the photoactive components with the spectrum of the sun. While the possibility of borrowing ideas about light-harvesting aggregates from nature in order to improve the efficiency of solar energy conversion is quite attractive, progress to date is hindered by incomplete understanding of aggregate internal structure and its relation to excitonic states. In this Perspective, we describe our recent work on the hierarchal structure of self-assembled porphyrin aggregates that are similar to light-harvesting complexes of photosynthetic bacteria. We address the question of whether aggregation can be beneficial to dye-sensitized solar energy conversion and present promising results for a solar cell based on an abundant plant pigment that displays signatures of aggregation when adsorbed on TiO2.