Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2'-bipyridine)(CN)₄]²

The excited state dynamics of solvated [Fe(bpy)(CN)₄]^2-, where bpy = 2,2'-bipyridine, show significant sensitivity to the solvent Lewis acidity. Using a combination of optical absorption and X-ray emission transient spectroscopies, we have previously shown that the metal to ligand charge transfer (MLCT) excited state of [Fe(bpy)(CN)₄]^2- has a 19 picosecond lifetime and no discernable contribution from metal centered (MC) states in weak Lewis acid solvents, such as dimethyl sulfoxide and acetonitrile.^1,2 In the present work, we use the same combination of spectroscopic techniques to measure the MLCT excited state relaxation dynamics of [Fe(bpy)(CN)₄]^2- in water, a strong Lewis acid solvent. The charge-transfer excited state is now found to decay in less than 100 femtoseconds, forming a quasi-stable metal centered excited state with a 13 picosecond lifetime. We find that this MC excited state has triplet (³MC) character, unlike other reported six-coordinate Fe(ii)-centered coordination compounds, which form MC quintet (⁵MC) states. The solvent dependent changes in excited state non-radiative relaxation for [Fe(bpy)(CN)₄]^2- allows us to infer the influence of the solvent on the electronic structure of the complex. Furthermore, the robust characterization of the dynamics and optical spectral signatures of the isolated ³MC intermediate provides a strong foundation for identifying ³MC intermediates in the electronic excited state relaxation mechanisms of similar Fe-centered systems being developed for solar applications.