Electronic structure and photophysics of a supermolecular iron complex having a long MLCT-state lifetime and panchromatic absorption
Ting Jiang, Yusong Bai, Peng Zhang, Qiwei Han, David B. Mitzi, Michael J. Therien
Abstract
Significance The main hurdle that prevents earth-abundant iron-based complexes from replacing environmentally unfriendly and expensive heavy metal [e.g., Ru(II), Os(II), Ir(III)] complexes in solar-energy conversion applications is the typical ultrashort (femtosecond timescale) charge-transfer state lifetime of Fe(II) chromophores. We provide a design roadmap to a generation of efficient iron-based photosensitizers and present an Fe(II) complex archetype, FeNHCPZn, which features a profoundly extended metal-to-ligand charge-transfer ( 3 MLCT) lifetime and a large transition-dipole moment difference between its ground and metal-to-ligand charge-transfer states. This supermolecular design promotes superior visible photon harvesting over classic metal complexes while assuring a triplet excited-state oxidation potential appropriate for charge injection into the conduction bands of common semiconductor electrode materials, highlighting its photosensitizing utility in dye-sensitized solar-cell architectures.