Sensitizing the Sensitizer: The Synthesis and Photophysical Study of Bodipy-Pt(II)(diimine)(dithiolate) Conjugates

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dc.contributor.authorLazarides, T.en
dc.contributor.authorMcCormick, T. M.en
dc.contributor.authorWilson, K. C.en
dc.contributor.authorLee, S.en
dc.contributor.authorMcCamant, D. W.en
dc.contributor.authorEisenberg, R.en
dc.date.accessioned2015-11-24T16:46:58Z
dc.date.available2015-11-24T16:46:58Z
dc.identifier.issn0002-7863-
dc.identifier.urihttps://olympias.lib.uoi.gr/jspui/handle/123456789/9126
dc.rightsDefault Licence-
dc.subjectdiimine-dithiolate complexesen
dc.subjectelectron-transferen
dc.subjectexcited-stateen
dc.subjectspectroscopic propertiesen
dc.subjectphotoinduced electronen
dc.subjectplatinum complexesen
dc.subjectsolar-cellsen
dc.subjectbodipy dyesen
dc.subjectfluorophoresen
dc.subjectderivativesen
dc.titleSensitizing the Sensitizer: The Synthesis and Photophysical Study of Bodipy-Pt(II)(diimine)(dithiolate) Conjugatesen
heal.abstractThe dyads 3, 4, and 6, combining the Bodipy chromophore with a Pt(bpy)(bdt) (bpy = 2,2'-bipyridine, bdt = 1,2-benzenedithiolate, 3 and 6) or a Pt(bpy)(mnt) (mnt = maleonitriledithiolate, 4) moiety, have been synthesized and studied by UV-vis steady-state absorption, transient absorption, and emission spectroscopies and cyclic voltammetry. Comparison of the absorption spectra and cyclic voltammograms of dyads 3, 4, and 6 and those of their model compounds 1a, 2, 5, and 7 shows that the spectroscopic and electrochemical properties of the dyads are essentially the sum of their constituent chromophores, indicating negligible interaction of the constituent chromophores in the ground state. However, emission studies on 3 and 6 show a complete absence of both Bodipy-based fluorescence and the characteristic luminescence of the Pt(bpy)(bdt) unit. Dyad 4 shows a weak Pt(mnt)-based emission. Transient absorption studies show that excitation of the dyads into the Bodipy-based (1)pi pi* excited state is followed by singlet energy transfer (SEnT) to the Pt(dithiolate)-based (MML)-M-1'CT (mixed metal-ligand to ligand charge transfer) excited state (tau(3)(SEnT) = 0.6 ps, tau(4)(SEnT) = 0.5 ps, and tau(6)(SEnT) = 1.6 ps), which undergoes rapid intersystem crossing to the (MMLL)-M-3'CT state due to the heavy Pt(II) ion. The (MMLL)-M-3'CT state is then depopulated by triplet energy transfer (TEnT) to the low-lying Bodipy-based 3 pi pi* excited state (tau(3)(TEnT) = 8.2 ps, tau(4)(TEnT) = 5 ps, and tau(6)(TEnT) = 160 ps). The transition assignments are supported by TD-DFT calculations. Both energy-transfer processes are shown to proceed via a Dexter electron exchange mechanism. The much longer time constants for dyad 6 relative to 3 are attributed to the significantly poorer coupling and resonance of charge-separated species that are intermediates in the electron exchange process.en
heal.accesscampus-
heal.fullTextAvailabilityTRUE-
heal.identifier.primaryDoi 10.1021/Ja1070366-
heal.identifier.secondary<Go to ISI>://000286544900030-
heal.identifier.secondaryhttp://pubs.acs.org/doi/pdfplus/10.1021/ja1070366-
heal.journalNameJ Am Chem Socen
heal.journalTypepeer reviewed-
heal.languageen-
heal.publicationDate2011-
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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