Synthesis And Photocatalytic Properties Of Ruthenium Supramolecular Catalysts

photoinduced organism oxygenation plays a vital role in organic substratestransformations. We are interested in combining a chromophore site and a catalyticfragment into one supramolecular system by employing different bridging ligandsfor improving photocatalytic reaction efficiencies. Herein we synthesized a noveland structurally simple chromophore-catalyst dyad of Ru-aqua complex and itschloro form complex. The complexes were characterized by1H NMR spectroscopyand high-resolution mass spectrometry (HR-MS). The Spectroscopic properties andelectrochemical characterizations were studied by UV-vis spectroscopy, cyclicvoltammetry (CV) and differential pulse voltammetry (DPV). Under visible lightirradiation and in the presence of a sacrificial electron acceptor, the both complexesoxidized the sulfide into corresponding sulfoxide with high efficiency and100%product selectivity in neutral aqueous solution. An isotopic labeling experimentdemonstrated the oxygen atom transfer from the water to the substrate and a catalyticmechanism involving the formation of active intermediate Ru(IV)=O was proposedby experiment results.The theme of this thesis is the development of supramolecular system withRu-based complexes, three supramolecular compounds:([RuII(bpy)3RuII(tpy)]-(pic)2-Cl),([RuII(bpy)3RuII(tpy)](pic)2-H2O),([RuII(bpy)3RuII(tpy)](pic)2-I)thatcapable of catalyzing the oxidation of water to produce oxygen were also synthesized.Their characteristic is a Ru center ([RuII(bpy)3]2+) as light harvesting antenna, anothercenter as catalyst, and the two part is connected by bridge ligand. We used catalystand photosensitizer connection through carbon carbon single bond made it as anorganic whole, Study on the properties of the supramolecular catalyst includingoptical properties, electrochemical properties and catalytic properties. From the figureof the production of oxygen with time perspective, the compounds ([RuII(bpy)3-RuII(tpy)](pic)2-Cl) may be just a pre-catalyst, The real catalyst should be the com-pound ([RuII(bpy)3RuII(tpy)](pic)2-I), and ([RuII(bpy)3RuII(tpy)](pic)2-H2O) is catalyst. Because the compounds ([RuII(bpy)3RuII(tpy)](pic)2-Cl) have a induction period.Molecular self-assembly display the activity of the supramolecular system bymolecular self-assembly formation is much stronger than the multicomponent system.In addition, an ion probe based on fluorescein was also synthesized, The probe isresponse for Cu2+on the UV absorption and Hg2+on the change of fluorescence. Ithas a great application prospect for ion recognition.