Enhancing Photocatalytic Hydrogen Generation: the Impact of the Peripheral Ligands in Ru/Pd and Ru/Pt Complexes. Issue 22 (27th March 2017)

• Record Type: Journal Article
• Authors: Das, Nivedita; Bindra, Gurmeet Singh; Paul, Avishek; Vos, Johannes G.; Schulz, Martin; Pryce, Mary T.
• Is Part Of: Chemistry. Volume 23:Issue 22(2017)
• Page Start: 5330
• Page End: 5337
• Publication Date: 2017-03-27
• Subjects: heterometallic complexes -- hydrogen -- photocatalysis -- photocatalytic hydrogen generation -- ruthenium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201605980
• Languages: English
• ISSNs: 0947-6539

Abstract

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 ]2 and [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. Abstract : Talkin' about H2 generation ! Photocatalytic hydrogen generation in bimetallic ruthenium complexes is dependent on the peripheral ligand, metal centre and amount of water in the reaction mixture (see scheme).