title: Encapsulating [FeFe]-hydrogenase model compounds in peptide hydrogels dramatically modifies stability and photochemistry.
abstract: A [FeFe]-hydrogenase model compound (µ-S(CH(2))(3)S)Fe(2)(CO)(4)(PMe(3))(2) [1] has been encapsulated in a low molecular weight (LMW) hydrogelator (Fmoc-Leu-Leu). Linear infrared absorption spectroscopy, gel melting and ultrafast time-resolved infrared spectroscopy experiments reveal significant contrasts in chemical environment and photochemistry between the encapsulated molecules and solution phase systems. Specifically, the gel provides a more rigid hydrogen bonding environment, which restricts isomerisation following photolysis while imparting significant increases in stability relative to a similarly aqueous solution. Since understanding and ultimately controlling the mechanistic role of ligands near Fe centres is likely to be crucial in exploiting artificial hydrogenases, these gels may offer a new option for future materials design involving catalysts.
authors.affiliation: Department of Physics, University of Strathclyde, SUPA, Glasgow, UK.
authors.forename: Pim W J M
authors.initials: PW
authors.lastname: Frederix
authors.forename: Rafal
authors.initials: R
authors.lastname: Kania
authors.forename: Joseph A
authors.initials: JA
authors.lastname: Wright
authors.forename: Dimitrios A
authors.initials: DA
authors.lastname: Lamprou
authors.forename: Rein V
authors.initials: RV
authors.lastname: Ulijn
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Pickett
authors.forename: Neil T
authors.initials: NT
authors.lastname: Hunt
mesh_terms: D004151:Dipeptides / Q000737:chemistry*; D005449:Fluorenes / Q000737:chemistry*; D020100:Hydrogels / Q000737:chemistry*; D006864:Hydrogenase / Q000737:chemistry*; D007506:Iron-Sulfur Proteins / Q000737:chemistry*; D055668:Photochemical Processes
chemical_list: C496789:9-fluorenylmethoxycarbonyl; D004151:Dipeptides; D005449:Fluorenes; D020100:Hydrogels; D007506:Iron-Sulfur Proteins; C038361:leucylleucine; C118830:iron hydrogenase; D006864:Hydrogenase