title: Cyclometalated Fe(II) complexes as sensitizers in dye-sensitized solar cells.
abstract: Dye-sensitized solar cells (DSSCs) often utilize transition metal-based chromophores for light absorption and semiconductor sensitization. Ru(II)-based dyes are among the most commonly used sensitizers in DSSCs. As ruthenium is both expensive and rare, complexes based on cheaper and more abundant iron could serve as a good alternative. In this study, we investigate Fe(II)-bis(terpyridine) and its cyclometalated analogues, in which pyridine ligands are systematically replaced by aryl groups, as potential photosensitizers in DSSCs. We employ density functional theory at the B3LYP/6-31G*,SDD level to obtain the ground state electronic structure of these complexes. Quantum dynamics simulations are utilized to study interfacial electron transfer between the Fe(II) photosensitizers and a titanium dioxide semiconductor. We find that cyclometalation stabilizes the singlet ground state of these complexes by 8-19 kcal/mol but reduces the electron density on the carboxylic acid attached to the aryl ring. The results suggest that cyclometalation provides a feasible route to increasing the efficiency of Fe(II) photosensitizers but that care should be taken in choosing the substitution position for the semiconductor anchoring group.
authors.affiliation: Department of Chemistry, North Carolina State University , Raleigh, North Carolina 27695, United States.
authors.forename: Sriparna
authors.initials: S
authors.lastname: Mukherjee
authors.forename: David N
authors.initials: DN
authors.lastname: Bowman
authors.forename: Elena
authors.initials: E
authors.lastname: Jakubikova