Electronic Structure and Photophysics of Low Spin d5 Metallocenes
Abstract
The electronic structure and photophysics of two low spin metallocenes, decamethylmanganocene (MnCp*2) and decamethylrhenocene (ReCp*2), were investigated to probe their promise as photoredox reagents. Computational studies support the assignment of 2E2 ground state configurations and low energy ligand-to-metal charge transfer transitions for both complexes. Weak emission is observed at room temperature for ReCp*2 with τ = 1.8 ns in pentane, whereas MnCp*2 is not emissive. Calculation of the excited state reduction potentials for both metallocenes reveal their potential potency as excited state reductants (E°'([MnCp*2]+/0*) = -3.38 V and E°'([ReCp*2]+/0*) = -2.61 V vs Fc+/0). Comparatively, both complexes exhibit mild potentials for photo-oxidative processes (E°'([MnCp*2]0*/-) = -0.18 V and E°'([ReCp*2]0*/-) = -0.20 V vs Fc+/0). These results showcase the rich electronic structure of low spin d5 metallocenes and their promise as excited state reductants.
Citation
May AM, Deegbey M, Edme K, Lee KJ, Perutz RN, Jakubikova E, Dempsey JL. Electronic Structure and Photophysics of Low Spin d5 Metallocenes. Inorg Chem. 2024 Jan 29;63(4):1858-1866. doi: 10.1021/acs.inorgchem.3c03451. Epub 2024 Jan 16. PMID: 38226604.