Azadipyrromethene cyclometalation in neutral RuII complexes: photosensitizers with extended near-infrared absorption for solar energy conversion applications

Abstract

In the on-going quest to harvest near-infrared (NIR) photons for energy conversion applications, a novel family of neutral ruthenium(II) sensitizers has been developed by cyclometalation of an azadipyrromethene chromophore. These rare examples of neutral ruthenium complexes based on polypyridine ligands exhibit an impressive panchromaticity achieved by the cyclometalation strategy, with strong light absorption in the 600–800 nm range that tails beyond 1100 nm in the terpyridine-based adducts. Evaluation of the potential for Dye-Sensitized Solar Cells (DSSC) and Organic Photovoltaic (OPV) applications is made through rationalization of the structure–property relationship by spectroscopic, electrochemical, X-ray structural and computational modelization investigations. Spectroscopic evidence for photo-induced charge injection into the conduction band of TiO₂ is also provided.