Synthesis and characterization of a novel type of ambident bridging ligands joining together the functional prerequisites for visible-light absorption, photoinduced electron transfer and catalytic proton reduction is presented. This class of compounds consists of a chromophoric 1,2-diimine-based π-acceptor site and a rigid polyaromatic dithiolate chelator. Due to the presence of a common conjugated linker moiety with an intrinsic two-electron redox reactivity and a suitable orbital coupling of the subunits, a favorable situation for vectorial multielectron transfer from attached electron donors to a catalytic acceptor site is provided. As an example for the application of this kind of bifunctional ligand systems, a [FeFe]-hydrogenase enzyme model compound is prepared and structurally characterized. Electrocatalytic hydrogen formation with this complex is demonstrated.
The catalytic acceleration of coupled two-electron / two-proton redox steps is a crucial functional feature for artificial photosynthesis and solar fuels research. For the first time, the building blocks for light absorption, multiple electron transfer and proton reduction have been successfully combined in a simple bio-inspired hydrogenase model system that can be readily further modified for solar photocatalytic applications.
► Novel bridging ligand with electronically coupled thiolate and diimine subunits. ► Biomimetic hydrogenase model compound with additional donor binding site. ► Non-innocent redox-relay for the acceleration of multielectron transfer processes.
Publication date: July 2013Source:Journal of Solid State Chemistry, Volume 203 Author(s): S. Kumar , K. Singh , M. Miclau , Ch. Simon , C. Martin , A. Maignan The change from antiferromagnetism induced ferroelectricity to spin glass ferroelectric relaxor has been studied along the ... more
Publication date: July 2013Source:Journal of Solid State Chemistry, Volume 203 Author(s): Brian B. Kitchen , Nina Verdal , Terrence J. Udovic , John J. Rush , Michael R. Hartman , Daniel J. DeVries To investigate the previously reported low-temperature phase transition in rubidium ... more
Publication date: July 2013Source:Journal of Solid State Chemistry, Volume 203 Author(s): T. Sasikala , L. Rama Moorthy , A. Mohan Babu , T. Srinivasa Rao The present work reports the absorption, photoluminescence and decay properties of singly doped Dy3+ and co-doped Dy3+/Tm3+ ions ... more
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