Rubrene: The interplay between intramolecular and intermolecular interactions determines the planarization of its tetracene core in the solid state

Handle URI:
http://hdl.handle.net/10754/558300
Title:
Rubrene: The interplay between intramolecular and intermolecular interactions determines the planarization of its tetracene core in the solid state
Authors:
Sutton, Christopher; Marshall, Michael S.; Sherrill, C. David; Risko, Chad; Bredas, Jean-Luc ( 0000-0001-7278-4471 )
Abstract:
Rubrene is one of the most studied molecular semiconductors; its chemical structure consists of a tetracene backbone with four phenyl rings appended to the two central fused rings. Derivatization of these phenyl rings can lead to two very different solid-state molecular conformations and packings: One in which the tetracene core is planar and there exists substantive overlap among neighboring π-conjugated backbones; and another where the tetracene core is twisted and the overlap of neighboring π-conjugated backbones is completely disrupted. State-of-the-art electronic-structure calculations show for all isolated rubrene derivatives that the twisted conformation is more favorable (by -1.7 to -4.1 kcal mol-1), which is a consequence of energetically unfavorable exchange-repulsion interactions among the phenyl side groups. Calculations based on available crystallographic structures reveal that planar conformations of the tetracene core in the solid state result from intermolecular interactions that can be tuned through well-chosen functionalization of the phenyl side groups, and lead to improved intermolecular electronic couplings. Understanding the interplay of these intramolecular and intermolecular interactions provides insight into how to chemically modify rubrene and similar molecular semiconductors to improve the intrinsic materials electronic properties.
KAUST Department:
Solar and Photovoltaic Engineering Research Center (SPERC); Physical Sciences and Engineering (PSE) Division
Citation:
Rubrene: The interplay between intramolecular and intermolecular interactions determines the planarization of its tetracene core in the solid state 2015:150615105527002 Journal of the American Chemical Society
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
Issue Date:
15-Jun-2015
DOI:
10.1021/jacs.5b04066
Type:
Article
ISSN:
0002-7863; 1520-5126
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/jacs.5b04066
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Solar and Photovoltaic Engineering Research Center (SPERC)

Full metadata record

DC FieldValue Language
dc.contributor.authorSutton, Christopheren
dc.contributor.authorMarshall, Michael S.en
dc.contributor.authorSherrill, C. Daviden
dc.contributor.authorRisko, Chaden
dc.contributor.authorBredas, Jean-Lucen
dc.date.accessioned2015-06-21T09:30:19Zen
dc.date.available2015-06-21T09:30:19Zen
dc.date.issued2015-06-15en
dc.identifier.citationRubrene: The interplay between intramolecular and intermolecular interactions determines the planarization of its tetracene core in the solid state 2015:150615105527002 Journal of the American Chemical Societyen
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.doi10.1021/jacs.5b04066en
dc.identifier.urihttp://hdl.handle.net/10754/558300en
dc.description.abstractRubrene is one of the most studied molecular semiconductors; its chemical structure consists of a tetracene backbone with four phenyl rings appended to the two central fused rings. Derivatization of these phenyl rings can lead to two very different solid-state molecular conformations and packings: One in which the tetracene core is planar and there exists substantive overlap among neighboring π-conjugated backbones; and another where the tetracene core is twisted and the overlap of neighboring π-conjugated backbones is completely disrupted. State-of-the-art electronic-structure calculations show for all isolated rubrene derivatives that the twisted conformation is more favorable (by -1.7 to -4.1 kcal mol-1), which is a consequence of energetically unfavorable exchange-repulsion interactions among the phenyl side groups. Calculations based on available crystallographic structures reveal that planar conformations of the tetracene core in the solid state result from intermolecular interactions that can be tuned through well-chosen functionalization of the phenyl side groups, and lead to improved intermolecular electronic couplings. Understanding the interplay of these intramolecular and intermolecular interactions provides insight into how to chemically modify rubrene and similar molecular semiconductors to improve the intrinsic materials electronic properties.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/jacs.5b04066en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jacs.5b04066.en
dc.titleRubrene: The interplay between intramolecular and intermolecular interactions determines the planarization of its tetracene core in the solid stateen
dc.typeArticleen
dc.contributor.departmentSolar and Photovoltaic Engineering Research Center (SPERC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalJournal of the American Chemical Societyen
dc.eprint.versionPost-printen
dc.contributor.institutionSchool of Chemistry and Biochemistry and Center for Organic Photonics and Electronics Georgia Institute of Technology Atlanta, Georgia 30332-0400 USAen
dc.contributor.institutionDepartment of Chemistry and Center for Applied Energy Research University of Kentucky Lexington, Kentucky 40506-0055 USAen
kaust.authorBredas, Jean-Lucen
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.