Effect of bulky substituents on thiopyrylium polymethine aggregation in the solid state: A theoretical evaluation of the implications for all-optical switching applications

Handle URI:
http://hdl.handle.net/10754/563869
Title:
Effect of bulky substituents on thiopyrylium polymethine aggregation in the solid state: A theoretical evaluation of the implications for all-optical switching applications
Authors:
Gieseking, Rebecca L.; Mukhopadhyay, Sukrit; Risko, Chad; Marder, Seth R.; Bredas, Jean-Luc ( 0000-0001-7278-4471 )
Abstract:
Polymethine dyes in dilute solutions display many of the optical properties required for all-optical switching applications. However, in thin films, aggregation and polymethine-counterion interactions can substantially modify their properties and limit their utility. Here, we examine the impact of a series of bulky substituents on the solid-state molecular packing of thiopyrylium polymethines by using a theoretical approach combining molecular-dynamics simulations and quantum-chemical calculations. Importantly, it is found that the positions of the substituents near the center and/or ends of the dye determine the extent to which aggregation is reduced; in particular, substituents near the polymethine center primarily modify the type of aggregation that is observed, while substituents near the polymethine ends reduce aggregation and aid in maintaining solution-like properties in the solid state. Our theoretical study elucidates relationships between molecular structure and bulk optical properties and provides design guidelines for all-optical switching materials.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; Materials Science and Engineering Program; Solar and Photovoltaic Engineering Research Center (SPERC)
Publisher:
American Chemical Society (ACS)
Journal:
Chemistry of Materials
Issue Date:
25-Nov-2014
DOI:
10.1021/cm5028755
Type:
Article
ISSN:
08974756
Sponsors:
This work was supported by the AFOSR MURI program (FA9550-10-1-0558) within the Center for Organic Materials for All-Optical Switching (COMAS). We gratefully acknowledge stimulating discussions with Drs. S. Barlow, J.M. Hales, and J.W. Perry.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Materials Science and Engineering Program; Solar and Photovoltaic Engineering Research Center (SPERC)

Full metadata record

DC FieldValue Language
dc.contributor.authorGieseking, Rebecca L.en
dc.contributor.authorMukhopadhyay, Sukriten
dc.contributor.authorRisko, Chaden
dc.contributor.authorMarder, Seth R.en
dc.contributor.authorBredas, Jean-Lucen
dc.date.accessioned2015-08-03T12:17:40Zen
dc.date.available2015-08-03T12:17:40Zen
dc.date.issued2014-11-25en
dc.identifier.issn08974756en
dc.identifier.doi10.1021/cm5028755en
dc.identifier.urihttp://hdl.handle.net/10754/563869en
dc.description.abstractPolymethine dyes in dilute solutions display many of the optical properties required for all-optical switching applications. However, in thin films, aggregation and polymethine-counterion interactions can substantially modify their properties and limit their utility. Here, we examine the impact of a series of bulky substituents on the solid-state molecular packing of thiopyrylium polymethines by using a theoretical approach combining molecular-dynamics simulations and quantum-chemical calculations. Importantly, it is found that the positions of the substituents near the center and/or ends of the dye determine the extent to which aggregation is reduced; in particular, substituents near the polymethine center primarily modify the type of aggregation that is observed, while substituents near the polymethine ends reduce aggregation and aid in maintaining solution-like properties in the solid state. Our theoretical study elucidates relationships between molecular structure and bulk optical properties and provides design guidelines for all-optical switching materials.en
dc.description.sponsorshipThis work was supported by the AFOSR MURI program (FA9550-10-1-0558) within the Center for Organic Materials for All-Optical Switching (COMAS). We gratefully acknowledge stimulating discussions with Drs. S. Barlow, J.M. Hales, and J.W. Perry.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleEffect of bulky substituents on thiopyrylium polymethine aggregation in the solid state: A theoretical evaluation of the implications for all-optical switching applicationsen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentMaterials Science and Engineering Programen
dc.contributor.departmentSolar and Photovoltaic Engineering Research Center (SPERC)en
dc.identifier.journalChemistry of Materialsen
dc.contributor.institutionSchool of Chemistry and Biochemistry, Center for Organic Materials for All-Optical Switching, Georgia Institute of TechnologyAtlanta, GA, United Statesen
dc.contributor.institutionDow Chemical CompanyMidland, MI, United Statesen
dc.contributor.institutionDepartment of Chemistry and Center for Applied Energy Research (CAER), University of KentuckyLexington, KY, United Statesen
kaust.authorBredas, Jean-Lucen
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