Photo‐ and Electrochemical Properties of a CO2 Reducing Ruthenium–Rhenium Quaterpyridine‐Based Catalyst. Issue 3 (27th February 2018)

• Record Type: Journal Article
• Authors: Frayne, Liam; Das, Nivedita; Paul, Avishek; Amirjalayer, Saeed; Buma, Wybren J.; Woutersen, Sander; Long, Conor; Vos, Johannes G.; Pryce, Mary T.
• Is Part Of: ChemPhotoChem. Volume 2:Issue 3(2018)
• Page Start: 323
• Page End: 331
• Publication Date: 2018-02-27
• Subjects: carbon dioxide reduction -- photocatalysis -- picosecond time-resolved infrared spectroscopy -- quantum chemical calculations; Photochemistry -- Periodicals; Periodicals; Electronic journals; 541.35
• DOI: 10.1002/cptc.201700197
• Languages: English
• ISSNs: 2367-0932

Abstract

Abstract: The bridging ligand 2, 2′, 5′, 3′′, 6′′, 2′′′‐quaterpyridine was utilised to tether [(bpy)2 Ru] 2+ and [Re(CO)3 Cl] subunits for the purpose of photocatalytic CO2 reduction. The photophysics and electrochemistry of the complex and associated mononuclear species are reported herein, in addition to photocatalytic, picosecond time‐resolved infrared and computational studies. Photophysical, time‐resolved IR, and electrochemical data together with quantum chemical calculations indicate weak communication between the two metal centres. As a result of the electron‐withdrawing effect of the ligand on both the Ru and Re subunits, the reducing power of the photosensitiser and catalytic unit were significantly attenuated relative to the intermolecular approach utilising [(bpy)3 Ru] 2+ and (bpy)Re(CO)3 Cl. Abstract : Double your money : The bridging ligand 2, 2′, 5′, 3′′, 6′′, 2′′′‐quaterpyridine was utilised to tether [(bpy)2 Ru] 2+ and [Re(CO)3 Cl] subunits as part of an Ru–Re intramolecular assembly for the purpose of photocatalytic CO2 reduction. Photocatalysis studies indicated that this intramolecular approach generated less CO. Spectroscopic and electrochemical data together with quantum chemical calculations indicate weak communication between the two metal centres.