title: Enhancing Photocatalytic Hydrogen Generation: the Impact of the Peripheral Ligands in Ru/Pd and Ru/Pt Complexes.
abstract: The synthesis, photophysical properties and photocatalytic efficiency of a range of novel supramolecular assemblies of the type [Ru(dceb)2(μ-bisbpy)MCl2][PF6]2and [Ru(bpy)2(μ-bisbpy)MCl2][PF6]2(M=Pd or Pt, dceb=diethyl 2,2'-bipyridine-4,4'-dicarboxylate, bpy=2,2'-bipyridine and bisbpy=2,2':5',3'':6'',2'''-quaterpyridine) are reported. Photocatalytic hydrogen generation was dependent on the nature of the peripheral ligand, on the catalytic centre and on the amount of water present in the photocatalytic mixture. The best catalytic conditions were obtained with the dceb peripheral ligand (turnover numbers up to 513 after 18 h). The experimental data and DFT calculations on both the bpy- and dceb-based compounds indicated that the peripheral dceb ligands participated in the photocatalytic process.
authors.affiliation: Strategic Research Cluster for Solar Energy Conversion, School of Chemical Sciences, Dublin City University, Dublin, 9, Ireland.
authors.forename: Nivedita
authors.initials: N
authors.lastname: Das
authors.affiliation: Strategic Research Cluster for Solar Energy Conversion, School of Chemical Sciences, Dublin City University, Dublin, 9, Ireland.|Current address: Exigence Technologies, Inc., 200-135 Innovation Drive, Winnipeg, Manitoba, R3T 6A8, Canada.
authors.forename: Gurmeet Singh
authors.initials: GS
authors.lastname: Bindra
authors.affiliation: Strategic Research Cluster for Solar Energy Conversion, School of Chemical Sciences, Dublin City University, Dublin, 9, Ireland.
authors.forename: Avishek
authors.initials: A
authors.lastname: Paul
authors.affiliation: Strategic Research Cluster for Solar Energy Conversion, School of Chemical Sciences, Dublin City University, Dublin, 9, Ireland.
authors.forename: Johannes G
authors.initials: JG
authors.lastname: Vos
authors.affiliation: Friedrich Schiller University Jena, Institute of Physical Chemistry, Helmholtzweg 4, 07743, Jena, Germany.|Leibniz Institute of Photonic Technology (IPHT), Albert-Einstein-Strasse 9, 07745, Jena, Germany.
authors.forename: Martin
authors.identifier: http://orcid.org/0000-0003-4989-5207
authors.initials: M
authors.lastname: Schulz
authors.affiliation: Strategic Research Cluster for Solar Energy Conversion, School of Chemical Sciences, Dublin City University, Dublin, 9, Ireland.
authors.forename: Mary T
authors.identifier: http://orcid.org/0000-0003-2270-2452
authors.initials: MT
authors.lastname: Pryce
keywords: heterometallic complexes; hydrogen; photocatalysis; photocatalytic hydrogen generation; ruthenium