A Series of Supramolecular Complexes for Solar Energy Conversion via Water Reduction to Produce Hydrogen: An Excited State Kinetic Analysis of Ru(II),Rh(III),Ru(II) Photoinitiated Electron Collectors

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dc.contributor.authorWhite, Travis A.en
dc.contributor.authorKnoll, Jessica D.en
dc.contributor.authorArachchige, Shamindri M.en
dc.contributor.authorBrewer, Karen J.en
dc.contributor.departmentChemistryen
dc.date.accessed2014-01-06en
dc.date.accessioned2014-01-15T14:16:36Zen
dc.date.available2014-01-15T14:16:36Zen
dc.date.issued2011-12-27en
dc.description.abstractMixed-metal supramolecular complexes have been designed that photochemically absorb solar light, undergo photoinitiated electron collection and reduce water to produce hydrogen fuel using low energy visible light. This manuscript describes these systems with an analysis of the photophysics of a series of six supramolecular complexes, [{(TL)2Ru(dpp)}2RhX2](PF6)5 with TL = bpy, phen or Ph2phen with X = Cl or Br. The process of light conversion to a fuel requires a system to perform a number of complicated steps including the absorption of light, the generation of charge separation on a molecular level, the reduction by one and then two electrons and the interaction with the water substrate to produce hydrogen. The manuscript explores the rate of intramolecular electron transfer, rate of quenching of the supramolecules by the DMA electron donor, rate of reduction of the complex by DMA from the 3MLCT excited state, as well as overall rate of reduction of the complex via visible light excitation. Probing a series of complexes in detail exploring the variation of rates of important reactions as a function of sub-unit modification provides insight into the role of each process in the overall efficiency of water reduction to produce hydrogen. The kinetic analysis shows that the complexes display different rates of excited state reactions that vary with TL and halide. The role of the MLCT excited state is elucidated by this kinetic study which shows that the 3MLCT state and not the 3MMCT is likely that key contributor to the photoreduction of these complexes. The kinetic analysis of the excited state dynamics and reactions of the complexes are important as this class of supramolecules behaves as photoinitiated electron collectors and photocatalysts for the reduction of water to hydrogen.en
dc.description.versionPublished versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationWhite, Travis A.; Knoll, Jessica D.; Arachchige, Shamindri M.; Brewer, Karen J. 2012. "A Series of Supramolecular Complexes for Solar Energy Conversion via Water Reduction to Produce Hydrogen: An Excited State Kinetic Analysis of Ru(II),Rh(III),Ru(II) Photoinitiated Electron Collectors." Materials 2012, 5(1), 27-46; doi:10.3390/ma5010027.en
dc.identifier.doihttps://doi.org/10.3390/ma5010027en
dc.identifier.issn1996-1944en
dc.identifier.urihttp://hdl.handle.net/10919/24850en
dc.identifier.urlhttp://www.mdpi.com/1996-1944/5/1/27en
dc.language.isoenen
dc.publisherMDPIen
dc.rightsCreative Commons Attribution 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.subjectintramolecular electron transferen
dc.subjectphotoinitiated electron collectionen
dc.subjectsupramolecular photocatalysisen
dc.subjectexcited state quenchingen
dc.subjecthydrogen productionen
dc.titleA Series of Supramolecular Complexes for Solar Energy Conversion via Water Reduction to Produce Hydrogen: An Excited State Kinetic Analysis of Ru(II),Rh(III),Ru(II) Photoinitiated Electron Collectorsen
dc.title.serialMaterialsen
dc.typeArticle - Refereeden
dc.type.dcmitypeTexten

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