Synthesis and Characterization of Cyclopentadithiophene Heterofulvenes: Design Tools for Light-Activated Processes

The development of new materials for solar-to-energy conversion should consider stability, ease of fabrication, and beneficial photophysical properties. In this context, a set of novel π-conjugated building blocks, with phospha- and arsaalkenes possessing a unique dithienyl annulated heterofulvenoid core, have been prepared as air- and moisture-stable sensitizers. These compounds unify electron-donor and -acceptor moieties, making them potential candidates for light-harvesting applications. Optical characterization of these systems was performed by steady-state and time-resolved absorption spectroscopy, supported by time-dependent DFT calculations. Tuning of the optical properties of these systems can be achieved by varying the pnictogen element at the bridgehead position, giving a bathochromic shift of ≈40 nm and coordinating the phosphaalkene towards gold Au^I centers. The latter results in a ≈2000-fold extension of the ≈10 ps lifetime of uncoordinated systems well into the ns regime.