Photocatalytic Properties And Electronic Effects Of Incorporation Bis(Acetylacetonato) Ruthenium(?) Complexes Bidentate Nitrogen And Sulfur Ancillaries

With the continuous development of new energy technologies,research on hydrogen production by photocatalytic water oxidation is a hot spot but also a difficult point in nowadays.The design and synthesis of highly active and selective photocatalyst is the key to produce hydrogen from water economically and efficiently.Due to its rich valences and obvious absorption peak in the near infrared region,Ru(acac)₃ was used to synthesize ruthenium acetylacetonate derivatives.These complexes usually have conjugated ligands(N^N,S^S)showing good electron transport effect.Photocatalytic properties of the ruthenium acetylacetonate complexes for hydrolysis of water to produce hydrogen were tested.Treatment of Ru(acac)₃ with nitrile ligands gave complexes containing two chelating rings:[(acac)₂Ru^?(CH₃CN)₂],[(acac)₂Ru^?(CH₃CH₂CH₂CN)₂](1)and[(acac)₂Ru^?(Ph CN)₂](2).Reaction of[(acac)₂Ru^?(CH₃CN)₂]with bidentate nitrogen and sulfur ligands(4,4'-dimethyl-2,2'-bipyridine,o-phenanthroline,o-phenylenediamine,4-bromo-o-phenylenediamine,Na[S₂CNMe₂])yielded complexes containing three chelating rings:[(acac)₂Ru^?(dimbpy)](PF₆)(3),[(acac)₂Ru^?(phen)](4),[(acac)₂Ru^?(1,2-(NH)₂C₆H₄)](5),[(acac)₂Ru^?(1,2-(NH)₂C₆H₃-4-Br)](6)and[(acac)₂Ru^?(S₂CNMe₂)](7).Treatment of Ru(acac-F₃)₃ with acetonitrile in the presence of CF₃SO₃H obtained a compound with one chelating ring:[(acac-CF₃)Ru^?(CH₃CN)₄](CF₃SO₃)(8).Reaction of Ru(DMSO)₄Cl₂with acac H in the presence of triethylamine gave a compound with one chelating ring:[(acac)Ru^?(DMSO)₃Cl](9).All complexes were characterized by NMR,FT-IR,UV-vis and fluorescence spectroscopies,and the structures of complexes 1?9 have been well established by X-ray crystallography.The electronchemical properties of all compounds and photocatalytic properties for hydrogen production by water hydrolysis of complexes3?7 under visible light(?>420 nm)were also investigated.