Picosecond to Nanosecond Manipulation of Excited-State Lifetimes in Complexes with an FeII to TiIV Metal-to-Metal Charge Transfer: The Role of Ferrocene Centered Excited States

Time-resolved transient absorption spectroscopy and computational analysis of D−π–A complexes comprising FeII donors and TiIV acceptors with the general formula RCp2Ti(C2Fc)2 (where RCp = Cp*, Cp, and MeOOCCp) and TMSCp2Ti(C2Fc)(C2R) (where R = Ph or CF3) are reported. The transient absorption spectra are consistent with an FeIII/TiIII metal-to-metal charge-transfer (MMCT) excited state for all complexes. Thus, excited-state decay is assigned to back-electron transfer (BET), the lifetime of which ranges from 18.8 to 41 ps. Though spectroscopic analysis suggests BET should fall into the Marcus inverted regime, the observed kinetics are not consistent with this assertion. TDDFT calculations reveal that the singlet metal-to-metal charge-transfer (1MMCT) excited state for the FeII/TiIV complexes is not purely MMCT in nature but is contaminated with the higher-energy 1Fc (d-d) state. For the diferrocenyl complexes, RCp2Ti(C2Fc)2, the ratio of MMCT to Fc centered character ranges from 57:43 for the Cp* complex ...