Improving the Stability of Organic Semiconductors: Distortion Energy versus Aromaticity in Substituted Bistetracene

Handle URI:
http://hdl.handle.net/10754/622759
Title:
Improving the Stability of Organic Semiconductors: Distortion Energy versus Aromaticity in Substituted Bistetracene
Authors:
Thomas, Simil ( 0000-0002-8069-4940 ) ; Ly, Jack; Zhang, Lei; Briseno, Alejandro L.; Bredas, Jean-Luc ( 0000-0001-7278-4471 )
Abstract:
Polycyclic aromatic hydrocarbons (PAHs) have been widely explored as molecular semiconductors in organic electronic devices such as field-effect transistors or solar cells. However, their tendency to undergo photooxidation is a primary limitation to their practical applications. Bistetracene derivatives have recently been demonstrated to possess much larger photo oxidation stability than the widely investigated pentacene and rubrene, while maintaining high charge-carrier mobilities. Here, using several levels of density functional theory, we identify the origin of the increased stability of bistetracene with respect to molecular oxygen by systematically investigating the [4 + 2] cycloaddition (Diels Alder) photooxidation reaction mechanism. Importantly, our computational results indicate that endoperoxide formation in bis(2-(trimethylsilyl)ethynyl) bistetracene (BT) occurs not on the ring with least aromaticity, but rather on the ring with smallest distortion energy. This feature was subsequently confirmed by experimental NMR analyses. The oxidation activation barriers of bistetracene, pentacene, and rubrene are found to be 17.7, 13.6, and 14.4 kcal/mol, respectively, in agreement with the observed order of stability of these molecules with respect to oxidation reactions in solution. In the cases of BT and pentacene, the rates of electron transfer to create charged species (PAH(+) and O-2) are at least two orders of magnitude lower than that of the charge recombination process (back to PAH and O-2); for rubrene, both of these processes are calculated to be of the same order of magnitude, in agreement with experimental electron paramagnetic resonance spectroscopy observations.
KAUST Department:
Laboratory for Computational and Theoretical Chemistry of Advanced Materials; Physical Sciences and Engineering (PSE) Division; Solar and Photovoltaic Engineering Research Center (SPERC)
Citation:
Thomas S, Ly J, Zhang L, Briseno AL, Bredas J-L (2016) Improving the Stability of Organic Semiconductors: Distortion Energy versus Aromaticity in Substituted Bistetracene. Chemistry of Materials 28: 8504–8512. Available: http://dx.doi.org/10.1021/acs.chemmater.6b02552.
Publisher:
American Chemical Society (ACS)
Journal:
Chemistry of Materials
Issue Date:
15-Nov-2016
DOI:
10.1021/acs.chemmater.6b02552
Type:
Article
ISSN:
0897-4756; 1520-5002
Sponsors:
This work was supported by King Abdullah University of Science and Technology (KAUST) and by ONR-Global (Award No. N62909-15-1-2003). We are grateful to the KAUST Supercomputing Laboratory and the KAUST IT Research Computing Team for providing continuous assistance as well as computational and storage resources. J.L. acknowledges funding from the National Science Foundation (DMR-1508627); L.Z. thanks the Office of Naval Research (N000147-14-1-0053); S.T. thanks Dr. Manjaly J. Ajitha for useful discussions.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.chemmater.6b02552
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.authorThomas, Similen
dc.contributor.authorLy, Jacken
dc.contributor.authorZhang, Leien
dc.contributor.authorBriseno, Alejandro L.en
dc.contributor.authorBredas, Jean-Lucen
dc.date.accessioned2017-01-29T13:51:37Z-
dc.date.available2017-01-29T13:51:37Z-
dc.date.issued2016-11-15en
dc.identifier.citationThomas S, Ly J, Zhang L, Briseno AL, Bredas J-L (2016) Improving the Stability of Organic Semiconductors: Distortion Energy versus Aromaticity in Substituted Bistetracene. Chemistry of Materials 28: 8504–8512. Available: http://dx.doi.org/10.1021/acs.chemmater.6b02552.en
dc.identifier.issn0897-4756en
dc.identifier.issn1520-5002en
dc.identifier.doi10.1021/acs.chemmater.6b02552en
dc.identifier.urihttp://hdl.handle.net/10754/622759-
dc.description.abstractPolycyclic aromatic hydrocarbons (PAHs) have been widely explored as molecular semiconductors in organic electronic devices such as field-effect transistors or solar cells. However, their tendency to undergo photooxidation is a primary limitation to their practical applications. Bistetracene derivatives have recently been demonstrated to possess much larger photo oxidation stability than the widely investigated pentacene and rubrene, while maintaining high charge-carrier mobilities. Here, using several levels of density functional theory, we identify the origin of the increased stability of bistetracene with respect to molecular oxygen by systematically investigating the [4 + 2] cycloaddition (Diels Alder) photooxidation reaction mechanism. Importantly, our computational results indicate that endoperoxide formation in bis(2-(trimethylsilyl)ethynyl) bistetracene (BT) occurs not on the ring with least aromaticity, but rather on the ring with smallest distortion energy. This feature was subsequently confirmed by experimental NMR analyses. The oxidation activation barriers of bistetracene, pentacene, and rubrene are found to be 17.7, 13.6, and 14.4 kcal/mol, respectively, in agreement with the observed order of stability of these molecules with respect to oxidation reactions in solution. In the cases of BT and pentacene, the rates of electron transfer to create charged species (PAH(+) and O-2) are at least two orders of magnitude lower than that of the charge recombination process (back to PAH and O-2); for rubrene, both of these processes are calculated to be of the same order of magnitude, in agreement with experimental electron paramagnetic resonance spectroscopy observations.en
dc.description.sponsorshipThis work was supported by King Abdullah University of Science and Technology (KAUST) and by ONR-Global (Award No. N62909-15-1-2003). We are grateful to the KAUST Supercomputing Laboratory and the KAUST IT Research Computing Team for providing continuous assistance as well as computational and storage resources. J.L. acknowledges funding from the National Science Foundation (DMR-1508627); L.Z. thanks the Office of Naval Research (N000147-14-1-0053); S.T. thanks Dr. Manjaly J. Ajitha for useful discussions.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.chemmater.6b02552en
dc.titleImproving the Stability of Organic Semiconductors: Distortion Energy versus Aromaticity in Substituted Bistetraceneen
dc.typeArticleen
dc.contributor.departmentLaboratory for Computational and Theoretical Chemistry of Advanced Materialsen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentSolar and Photovoltaic Engineering Research Center (SPERC)en
dc.identifier.journalChemistry of Materialsen
dc.contributor.institutionDepartment of Polymer Science & Engineering, Conte Polymer Research Center, University of Massachusetts, Amherst, Massachusetts 01003, United Statesen
kaust.authorThomas, Similen
kaust.authorBredas, Jean-Lucen
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