NDLI: New Polyazine-Bridged Ru(II),Rh(III) and Ru(II),Rh(I) Supramolecular Photocatalysts for Water Reduction to Hydrogen Applicable for Solar Energy Conversion and Mechanistic Investigation of the Photocatalytic Cycle

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New Polyazine-Bridged Ru(II),Rh(III) and Ru(II),Rh(I) Supramolecular Photocatalysts for Water Reduction to Hydrogen Applicable for Solar Energy Conversion and Mechanistic Investigation of the Photocatalytic Cycle

Content Provider	Semantic Scholar
Author	Zhou, Rongwei
Copyright Year	2014
Abstract	The goal of this research is to test the design constraints of active dpp-bridged Ru II ,Rh III (dpp = 2,3-bis(2-pyridyl)pyrazine)) supramolecular photocatalysts for water reduction to H2 and provide mechanistic insights into the catalytic cycle. Two member of a new Ru II ,Rh III motifs with only one Rh‒Cl bond, [(bpy)2Ru(dpp)RhCl(tpy)](PF6)4 ( bpy = 2,2'-bipyridine, tpy = 2,2':6',2"-terpyridine) and [(bpy)2Ru(dpp)RhCl(tpm)](PF6)4, (tpm = tris(1-pyrazolyl)methane), and a cis-RhCl2 model system, [(bpy)2Ru(dpp)RhCl2(bpy)](PF6)3, were prepared. This new motif was to test whether two Rh‒Cl bonds on Rh III are required for the photocatalytic water reduction. 1 H NMR spectroscopic analysis of complexes prepared using deuterated ligands was used to characterize these three Ru II ,Rh III supramolecular complexes. Electrochemical studies suggested that replacing bpy with a tridentate ligand on Rh III shifts the Rh III/II and Rh II/I reduction couples positively, which can modulate the orbital energetics of the Rh III (dσ) LUMO (lowest-unoccupied molecular orbital). This substitute also changes the rate of ligand dissociation following the reduction of Rh III . In tpm and bpy systems, Rh II intermediate is more stable than that in the tpy system. All three complexes were good light absorbers in the visible region and weak emitters from their emissive Ru(dπ)→dpp(π) 3 MLCT (metal-to-ligand charge transfer) excited states at room temperature. The population of a low-lying 3 MMCT (metal-to-metal charge transfer) ES
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Alternate Webpage(s)	https://vtechworks.lib.vt.edu/bitstream/handle/10919/50832/Zhou_R_D_2014.pdf?isAllowed=y&sequence=1
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article

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