Computational Design of Cyclic Nitroxides as Efficient Redox Mediators for Dye-Sensitized Solar Cells

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dc.contributor.authorGryn'ova, Ganna
dc.contributor.authorBarakat, Jonathan
dc.contributor.authorBlinco, James P.
dc.contributor.authorBottle, Steven E
dc.contributor.authorCoote, Michelle
dc.date.accessioned2015-12-10T23:06:47Z
dc.date.issued2012
dc.date.updated2016-02-24T10:45:05Z
dc.description.abstractCyclic nitroxide radicals represent promising alternatives to the iodine-based redox mediator commonly used in dye-sensitized solar cells (DSSCs). To date DSSCs with nitroxide-based redox mediators have achieved energy conversion efficiencies of just over 5 % but efficiencies of over 15 % might be achievable, given an appropriate mediator. The efficacy of the mediator depends upon two main factors: it must reversibly undergo one-electron oxidation and it must possess an oxidation potential in a range of 0.600-0.850 V (vs. a standard hydrogen electrode (SHE) in acetonitrile at 25 °C). Herein, we have examined the effect that structural modifications have on the value of the oxidation potential of cyclic nitroxides as well as the reversibility of the oxidation process. These included alterations to the N-containing skeleton (pyrrolidine, piperidine, isoindoline, azaphenalene, etc.), as well as the introduction of different substituents (alkyl-, methoxy-, amino-, carboxy-, etc.) to the ring. Standard oxidation potentials were calculated using high-level ab initio methodology that was demonstrated to be very accurate (with a mean absolute deviation from experimental values of only 16 mV). An optimal value of 1.45 for the electrostatic scaling factor for UAKS radii in acetonitrile solution was obtained. Established trends in the values of oxidation potentials were used to guide molecular design of stable nitroxides with desired E°ox and a number of compounds were suggested for potential use as enhanced redox mediators in DSSCs.
dc.identifier.issn0947-6539
dc.identifier.urihttp://hdl.handle.net/1885/62808
dc.publisherWiley-VCH Verlag GMBH
dc.sourceChemistry, A European Journal
dc.subjectKeywords: Ab initio calculations; Ab initio methodology; Acetonitrile solutions; Computational design; Dye-Sensitized solar cell; Dye-sensitized solar cells; Experimental values; Isoindoline; Mean absolute deviations; Methoxy; Molecular design; Nitroxide radicals; ab initio calculations; dye-sensitized solar cells; electrochemistry; nitroxides; oxidation potential
dc.titleComputational Design of Cyclic Nitroxides as Efficient Redox Mediators for Dye-Sensitized Solar Cells
dc.typeJournal article
local.bibliographicCitation.issue24
local.bibliographicCitation.lastpage7593
local.bibliographicCitation.startpage7582
local.contributor.affiliationGryn'ova, Ganna, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationBarakat, Jonathan, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationBlinco, James P., Queensland University of Technology
local.contributor.affiliationBottle, Steven E, Queensland University of Technology
local.contributor.affiliationCoote, Michelle, College of Physical and Mathematical Sciences, ANU
local.contributor.authoremailu4031074@anu.edu.au
local.contributor.authoruidGryn'ova, Ganna, u4768988
local.contributor.authoruidBarakat, Jonathan, u4518421
local.contributor.authoruidCoote, Michelle, u4031074
local.description.embargo2037-12-31
local.description.notesImported from ARIES
local.identifier.absfor030399 - Macromolecular and Materials Chemistry not elsewhere classified
local.identifier.absfor030701 - Quantum Chemistry
local.identifier.absseo970103 - Expanding Knowledge in the Chemical Sciences
local.identifier.ariespublicationU4217927xPUB739
local.identifier.citationvolume18
local.identifier.doi10.1002/chem.201103598
local.identifier.scopusID2-s2.0-84861800415
local.identifier.thomsonID000304755700033
local.identifier.uidSubmittedByU4217927
local.type.statusPublished Version

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