Using sulfur bridge oxidation to control electronic coupling and photochemistry in covalent anthracene dimers
Entity
UAM. Departamento de Física de la Materia CondensadaPublisher
Royal Society of ChemistryDate
2019-01-01Citation
10.1039/C8SC05598J
Chemical Science 2019.10 (2019): 7561-7573
ISSN
2041-6539 (online); 2041-6520 (print)DOI
10.1039/C8SC05598JFunded by
This work was supported by the Basque Government (IT588-13) and the Spanish Government MINECO/FEDER (CT2016-80955-P). C. C. is indebted to the European Research Council (ERC-2016-STG-714870) for a postdoctoral contract. M. O. W. acknowledges support from the Natural Sciences and Engineering Research Council. C. J. B. acknowledges support from the National Science Foundation grant CHE-1800187Project
Gobierno de España. CT2016-80955-P; info:eu-repo/grantAgreement/EC/H2020/714870/EU//MMUSCLESEditor's Version
https://doi.org/10.1039/c8sc05598jSubjects
Bichromophores; Chromophore; Optical spectroscopy; Electronic structure theory; FísicaRights
© 2019 The Royal Society of ChemistryAbstract
Covalently tethered bichromophores provide an ideal proving ground to develop strategies for controlling excited state behavior in chromophore assemblies. In this work, optical spectroscopy and electronic structure theory are combined to demonstrate that the oxidation state of a sulfur linker between anthracene chromophores gives control over not only the photophysics but also the photochemistry of the molecules. Altering the oxidation state of the sulfur linker does not change the geometry between chromophores, allowing electronic effects between chromophores to be isolated. Previously, we showed that excitonic states in sulfur-bridged terthiophene dimers were modulated by electronic screening of the sulfur lone pairs, but that the sulfur orbitals were not directly involved in these states. In the bridged anthracene dimers that are the subject of the current paper, the atomic orbitals of the unoxidized S linker can actively mix with the anthracene molecular orbitals to form new electronic states with enhanced charge transfer character, different excitonic coupling, and rapid (sub-nanosecond) intersystem crossing that depends on solvent polarity. However, the fully oxidized SO2 bridge restores purely through-space electronic coupling between anthracene chromophores and inhibits intersystem crossing. Photoexcitation leads to either internal conversion on a sub-20 picosecond timescale, or to the creation of a long-lived emissive state that is the likely precursor of the intramolecular [4 + 4] photodimerization. These results illustrate how chemical modification of a single atom in the covalent bridge can dramatically alter not only the photophysics but also the photochemistry of molecules
Files in this item
Google Scholar:Cruz, Chad D.
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Yuan, Jennifer
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Climent, Clàudia
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Tierce, Nathan T.
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Christensen, Peter R.
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Chronister, Eric L.
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Casanova, David
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Wolf, Michael O.
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Bardeen, Christopher J.
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