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A Study of the Interactions between I/I3 Redox Mediators and Organometallic Sensitizing Dyes in Solar Cells
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry, Physical Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry, Physical Chemistry.
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2009 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 113, no 2, 783-790 p.Article in journal (Refereed) Published
Abstract [en]

Specific interactions of the I/I3 redox mediators with the reduced and oxidized dye, Ru(4,4′-dicarboxy-2,2′-bipyridyl)2(NCS)2, referred to as N3 or Ru(dcbpy)2(NCS)2, have been studied by means of density functional theory (DFT) with the focus on the charge transfer process involving {dye+ I} adducts; computations had been performed with a series of density functionals (gradient-corrected density functional BP86, and the hybrid density functionals B3LYP, MPW1K, B3PW1K, and MPW1PW91). Different pathways leading to {dye+ I} adducts have been studied. First, mechanistic insights into the interaction of I with RuIII(dcbpy)2(NCS)2 via an SCN ligand directly giving rise to RuII(dcbpy)2(NCS)2I⌉0 have been obtained with the distinctive S−I bonding. Second, the binding of I to the N3 dye cation via I−dcbpy interactions has been analyzed. We also report experimental and computational evidence that sheds light on the interaction of the redox mediator with bipyridyl moieties. Evidence for a charge transfer process in the presence of only one I anion in the outer coordination sphere of the ruthenium center has been identified. Finally, geometries and electronic structures of plausible intermediates have been computationally analyzed based on an inner-sphere interaction between the metal center and the redox mediator, including a two-step regeneration reaction: RuIII(dcbpy)2(NCS)2+ + I → RuIII(dcbpy)2(NCS)I⌉+ + SCN, followed by the interaction of a second I with the intermediate RuIII(dcbpy)2(NCS)I⌉+ complex. Conclusive evidence of a charge-transfer process that gives rise to the regenerated RuII complex, where I interacts with the intermediate RuIII(dcbpy)2(NCS)I⌉+ complex has been identified.

Place, publisher, year, edition, pages
2009. Vol. 113, no 2, 783-790 p.
National Category
Chemical Sciences
Research subject
Physical Chemistry
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URN: urn:nbn:se:uu:diva-87786DOI: 10.1021/jp810201cISI: 000262324600045OAI: oai:DiVA.org:uu-87786DiVA: diva2:133607
Available from: 2009-01-13 Created: 2009-01-13 Last updated: 2011-07-07Bibliographically approved

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Publisher's full texthttp://pubs.acs.org/doi/abs/10.1021/jp810201c

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Boschloo, GerritHagfeldt, Anders

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