Cyclometalated 6-Phenyl-2,2 '-bipyridyl (CNN) Platinum(II) Acetylide Complexes: Structure, Electrochemistry, Photophysics, and Oxidative-and Reductive-Quenching Studies

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dc.contributor.authorSchneider, J.en
dc.contributor.authorDu, P. W.en
dc.contributor.authorJarosz, P.en
dc.contributor.authorLazarides, T.en
dc.contributor.authorWang, X. Y.en
dc.contributor.authorBrennessel, W. W.en
dc.contributor.authorEisenberg, R.en
dc.date.accessioned2015-11-24T16:55:12Z
dc.date.available2015-11-24T16:55:12Z
dc.identifier.issn0020-1669-
dc.identifier.urihttps://olympias.lib.uoi.gr/jspui/handle/123456789/10272
dc.rightsDefault Licence-
dc.subjectphotocatalytic hydrogen evolutionen
dc.subjectphotoinduced electron-transferen
dc.subjectvisible-lighten
dc.subjectexcited-stateen
dc.subjecttemperature-dependenceen
dc.subjectnonradiative decayen
dc.subjectiridium complexesen
dc.subjectwateren
dc.subjectenergyen
dc.subjectliganden
dc.titleCyclometalated 6-Phenyl-2,2 '-bipyridyl (CNN) Platinum(II) Acetylide Complexes: Structure, Electrochemistry, Photophysics, and Oxidative-and Reductive-Quenching Studiesen
heal.abstractThree cyclometalated 6-phenyl-4-(p-R-phenyl)-2,2'-bipyridyl (CNN-Ph-R) Pt(II) acetylide complexes, Pt(CNN-Ph-R)(CCPh), where R = Me (1), COOMe (2), and P(O)(OEt)(2) (3), have been synthesized and studied. Compounds 1 and 3 have been structurally characterized by single crystal X-ray crystallography and are found to exhibit distorted square planar geometries about the Pt(II) ions. The electrochemical properties of the compounds, as determined by cyclic voltammetry, have also been examined. Complexes 1-3 are brightly emissive in fluid CH(2)Cl(2) solution and in the solid state with lambda(max)(em) of ca. 600 nm and lifetimes on the order of ca. 500 ns in fluid solution. The emissions are assigned to a (3)MLCT transition. The complexes undergo oxidative quenching by MV(2+) with quenching rates near the diffusion-controlled limit (k(q) similar to 1.4 x 10(10) M(-1) s(-1)) in CH(2)Cl(2) solution. Reductive-quenching experiments of complexes 1-3 by the amine donors N,N,N',N'-tetramethylphenylenediamine (TMPD), phenothiazine (PTZ), and N,N,N',N'-tetramethylbenzidine (TMB) follow Stern-Volmer behavior, with very fast quenching rates on the order of 10(9)-10(10) M(-1) s(-1) in CH(2)Cl(2) solution. When the complexes are employed as the sensitizer in multiple component systems containing MV(2+), TEOA, and colloidal Pt in aqueous media, approximately one turnover of H(2) (TN vs mol of chromophore) is produced per hour upon irradiation with lambda > 410 nm but only after at least a 2 h induction period.en
heal.accesscampus-
heal.fullTextAvailabilityTRUE-
heal.identifier.primaryDoi 10.1021/Ic801947v-
heal.identifier.secondary<Go to ISI>://000266046300007-
heal.identifier.secondaryhttp://pubs.acs.org/doi/pdfplus/10.1021/ic801947v-
heal.journalNameInorg Chemen
heal.journalTypepeer reviewed-
heal.languageen-
heal.publicationDate2009-
heal.publisherAmerican Chemical Societyen
heal.recordProviderΠανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείαςel
heal.typejournalArticle-
heal.type.elΆρθρο Περιοδικούel
heal.type.enJournal articleen

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