n-Dopants Based on Dimers of Benzimidazoline Radicals: Structures and Mechanism of Redox Reactions

Handle URI:
http://hdl.handle.net/10754/566137
Title:
n-Dopants Based on Dimers of Benzimidazoline Radicals: Structures and Mechanism of Redox Reactions
Authors:
Zhang, Siyuan; Naab, Benjamin D.; Jucov, Evgheni V.; Parkin, Sean; Evans, Eric G B; Millhauser, Glenn L.; Timofeeva, Tatiana V.; Risko, Chad; Bredas, Jean-Luc ( 0000-0001-7278-4471 ) ; Bao, Zhenan; Barlow, Stephen; Marder, Seth R.
Abstract:
Dimers of 2-substituted N,N'-dimethylbenzimidazoline radicals, (2-Y-DMBI)2 (Y=cyclohexyl (Cyc), ferrocenyl (Fc), ruthenocenyl (Rc)), have recently been reported as n-dopants for organic semiconductors. Here their structural and energetic characteristics are reported, along with the mechanisms by which they react with acceptors, A (PCBM, TIPS-pentacene), in solution. X-ray data and DFT calculations both indicate a longer C-C bond for (2-Cyc-DMBI)2 than (2-Fc-DMBI)2, yet DFT and ESR data show that the latter dissociates more readily due to stabilization of the radical by Fc. Depending on the energetics of dimer (D2) dissociation and of D2-to-A electron transfer, D2 reacts with A to form D+ and A- by either of two mechanisms, differing in whether the first step is endergonic dissociation or endergonic electron transfer. However, the D+/0.5D2 redox potentials-the effective reducing strengths of the dimers-vary little within the series (ca. -1.9V vs. FeCp2+/0) (Cp=cyclopentadienyl) due to cancelation of trends in the D+/0 potential and D2 dissociation energy. The implications of these findings for use of these dimers as n-dopants, and for future dopant design, are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
KAUST Department:
Physical Sciences and Engineering (PSE) Division
Publisher:
Wiley-Blackwell
Journal:
Chemistry - A European Journal
Issue Date:
18-Jun-2015
DOI:
10.1002/chem.201500611
Type:
Article
ISSN:
09476539
Is Supplemented By:
Zhang, S., Naab, B. D., Jucov, E. V., Parkin, S., Evans, E. G. B., Millhauser, G. L., … Marder, S. R. (2015). CCDC 1048481: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1460zb; DOI:10.5517/cc1460zb; HANDLE:http://hdl.handle.net/10754/624402; Zhang, S., Naab, B. D., Jucov, E. V., Parkin, S., Evans, E. G. B., Millhauser, G. L., … Marder, S. R. (2015). CCDC 1048482: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc14610d; DOI:10.5517/cc14610d; HANDLE:http://hdl.handle.net/10754/624403
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorZhang, Siyuanen
dc.contributor.authorNaab, Benjamin D.en
dc.contributor.authorJucov, Evgheni V.en
dc.contributor.authorParkin, Seanen
dc.contributor.authorEvans, Eric G Ben
dc.contributor.authorMillhauser, Glenn L.en
dc.contributor.authorTimofeeva, Tatiana V.en
dc.contributor.authorRisko, Chaden
dc.contributor.authorBredas, Jean-Lucen
dc.contributor.authorBao, Zhenanen
dc.contributor.authorBarlow, Stephenen
dc.contributor.authorMarder, Seth R.en
dc.date.accessioned2015-08-12T09:29:43Zen
dc.date.available2015-08-12T09:29:43Zen
dc.date.issued2015-06-18en
dc.identifier.issn09476539en
dc.identifier.doi10.1002/chem.201500611en
dc.identifier.urihttp://hdl.handle.net/10754/566137en
dc.description.abstractDimers of 2-substituted N,N'-dimethylbenzimidazoline radicals, (2-Y-DMBI)2 (Y=cyclohexyl (Cyc), ferrocenyl (Fc), ruthenocenyl (Rc)), have recently been reported as n-dopants for organic semiconductors. Here their structural and energetic characteristics are reported, along with the mechanisms by which they react with acceptors, A (PCBM, TIPS-pentacene), in solution. X-ray data and DFT calculations both indicate a longer C-C bond for (2-Cyc-DMBI)2 than (2-Fc-DMBI)2, yet DFT and ESR data show that the latter dissociates more readily due to stabilization of the radical by Fc. Depending on the energetics of dimer (D2) dissociation and of D2-to-A electron transfer, D2 reacts with A to form D+ and A- by either of two mechanisms, differing in whether the first step is endergonic dissociation or endergonic electron transfer. However, the D+/0.5D2 redox potentials-the effective reducing strengths of the dimers-vary little within the series (ca. -1.9V vs. FeCp2+/0) (Cp=cyclopentadienyl) due to cancelation of trends in the D+/0 potential and D2 dissociation energy. The implications of these findings for use of these dimers as n-dopants, and for future dopant design, are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.en
dc.publisherWiley-Blackwellen
dc.subjectDensity functional calculationsen
dc.subjectDopingen
dc.subjectReaction mechanismen
dc.subjectRedox chemistryen
dc.subjectStructure elucidationen
dc.titlen-Dopants Based on Dimers of Benzimidazoline Radicals: Structures and Mechanism of Redox Reactionsen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalChemistry - A European Journalen
dc.contributor.institutionSchool of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, GA 30332-0400 (USA)en
dc.contributor.institutionDepartments of Chemical Engineering and Chemistry, Stanford University, Stanford, CA 94303 (USA)en
dc.contributor.institutionDepartment of Chemistry, New Mexico Highlands University, Las Vegas, NM 87701 (USA)en
dc.contributor.institutionDepartment of Chemistry, University of Kentucky, Lexington, KY 40506 (USA)en
kaust.authorBredas, Jean-Lucen
dc.relation.isSupplementedByZhang, S., Naab, B. D., Jucov, E. V., Parkin, S., Evans, E. G. B., Millhauser, G. L., … Marder, S. R. (2015). CCDC 1048481: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1460zben
dc.relation.isSupplementedByDOI:10.5517/cc1460zben
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624402en
dc.relation.isSupplementedByZhang, S., Naab, B. D., Jucov, E. V., Parkin, S., Evans, E. G. B., Millhauser, G. L., … Marder, S. R. (2015). CCDC 1048482: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc14610den
dc.relation.isSupplementedByDOI:10.5517/cc14610den
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624403en
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