NDLI: Synthesis and properties of new mononuclear Ru(II)-based photocatalysts containing 4,4′-diphenyl-2,2′-bipyridyl ligands

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Sánchez, Sergio Coe, Benjamin J.
Description	Author Affiliation: Coe BJ ( School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK. b.coe@manchester.ac.uk.); Sánchez S ( School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK. b.coe@manchester.ac.uk.)
Abstract	The synthesis and characterisation of a series of eleven new 4,4′-diphenyl-2,2′-bipyridyl derivatives (N^N) with varying 4- or 3,5-substituents on the phenyl rings are reported. The molecular structures of two of these compounds, 4,4′-bis(3,5-diheptyloxyphenyl)-2,2′-bipyridyl and 4,4′-bis(3,5-di-4,4,5,5,5-pentafluoropentyloxyphenyl)-2,2′-bipyridyl are confirmed by X-ray crystallography. Fourteen neutral complexes $trans-Ru^{II}Cl_{2}(N\^N)(CO)_{2}$ are prepared by reacting the new proligands and three known ones with the polymeric precursor $[Ru^{II}Cl_{2}(CO)_{2}]_{n},$ and their optical and electrochemical properties are studied. Density functional theory (DFT) and time-dependent DFT calculations have been carried out on selected complexes in order to rationalise their electronic structures and absorption properties. The low energy electronic absorption bands have metal-to-ligand charge-transfer and ligand-to-ligand charge-transfer (LLCT) character, but these dominate only in the 4-substituted species. In the 3,5-disubstituted ones, intraligand charge-transfer (ILCT) within the bpy ligands becomes more important. The complexes show only irreversible reductive electrochemistry and no signs of polymerisation. The photocatalytic oxidation behaviour of selected $trans-Ru^{II}Cl_{2}(N\^N)(CO)_{2}$ complexes and their mono-aquo derivatives $[Ru^{II}(H_{2}O)(CO)_{2}Cl(N\^N)]^{+}$ with 4-methoxybenzyl alcohol is studied. Turnover numbers of up to ca. 130 are achieved when using $[Ru^{II}(bpy)_{3}]^{2+}$ (bpy = 2,2′-bipyridyl) as photosensitizer and $[Co^{III}(NH_{3})_{5}Cl]^{2+}$ as a sacrificial oxidant.
ISSN	14779226
Issue Number	12
Journal	Dalton Trans.
Volume Number	45
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2016-03-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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