Ultrafast Photodynamics of Cyano-Functionalized [FeFe] Hydrogenase Model Compounds

[FeFe] hydrogenases are efficient enzymes that produce hydrogen gas under mild conditions. Synthetic model compounds containing all CO or mixed CO/PMe₃ ligands were previously studied by us and others with ultrafast ultraviolet or visible pump-infrared probe spectroscopy in an effort to better understand the function and interactions of the active site with light. Studies of anionic species containing cyano groups, which more closely match the biological active site, have been elusive. In this work, two model compounds dissolved in room-temperature acetonitrile solution were examined: [Fe₂(micro-S₂C₃H₆)(CO)₄(CN)₂]^2- (1) and [Fe₂(micro-S₂C₂H₄)(CO)₄(CN)₂]^2- (2). These species exhibit long-lived transient signals consistent with loss of one CO ligand with potential isomerization of newly formed ground electronic state photoproducts, as previously observed with all-CO and CO/PMe₃-containing models. We find no evidence for fast (ca. 150 ps) relaxation seen in the all-CO and CO/PMe₃ compounds because of the absence of the metal-to-metal charge transfer band in the cyano-functionalized models. These results indicate that incorporation of cyano ligands may significantly alter the electronic properties and photoproducts produced immediately after photoexcitation, which may influence the catalytic activity of model compounds when attached to photosensitizers.