Dithieno[3,2-a:2',3'-c]phenazine-based Chemical Probe for Anions: A Spectroscopic Study of Binding

Handle URI:
http://hdl.handle.net/10754/552106
Title:
Dithieno[3,2-a:2',3'-c]phenazine-based Chemical Probe for Anions: A Spectroscopic Study of Binding
Authors:
El-Assaad, Tarek H.; Shiring, Stephen B.; Getmanenko, Yulia A.; Hallal, Kassem M.; Bredas, Jean-Luc ( 0000-0001-7278-4471 ) ; Marder, Seth R; Al-Sayah, Mohammad H.; Kaafarani, Bilal R
Abstract:
The synthesis of a new anion-responsive molecule N,N'-(2,5-bis(4-(tert-butyl)phenyl)dithieno[3,2-a:2',3'-c]phenazine-9,10-diyl)bis(4-methylbenzenesulfonamide) (1) is reported. The sensitivities of the spectroscopic properties of 1 in the presence of various anions were examined using UV-vis absorption spectroscopy, fluorescence and 1H NMR titration experiments. Strong binding of 1 to carboxylate, cyanide, fluoride and dihydrogen phosphate anions results in an increase in quantum yield for emission of 1, and changes in its 1H NMR chemical shifts. A significant electrostatic interaction of the tetrabutylammonium cation with 1, upon strong binding with the counter anion, was also indicated by the chemical shifts observed in the 1H NMR titrations. Binding constants of 1 to anions are also calculated based on the binding isotherms derived from NMR and UV-Vis titrations. DFT calculations show that the anion does not significantly impact the HOMO/LUMO levels (and subsequently the S0 -> S1 transition), but rather changes the strength of the S0 -> S2 transition, which accounts for the observed changes in the UV-vis spectra.
KAUST Department:
Solar and Photovoltaic Engineering Research Center
Citation:
Dithieno[3,2-a:2',3'-c]phenazine-based Chemical Probe for Anions: A Spectroscopic Study of Binding 2015 RSC Adv.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
RSC Adv.
Issue Date:
27-Apr-2015
DOI:
10.1039/C5RA01416F
Type:
Article
ISSN:
2046-2069
Additional Links:
http://pubs.rsc.org/en/Content/ArticleLanding/2015/RA/C5RA01416F
Appears in Collections:
Articles; Solar and Photovoltaic Engineering Research Center (SPERC)

Full metadata record

DC FieldValue Language
dc.contributor.authorEl-Assaad, Tarek H.en
dc.contributor.authorShiring, Stephen B.en
dc.contributor.authorGetmanenko, Yulia A.en
dc.contributor.authorHallal, Kassem M.en
dc.contributor.authorBredas, Jean-Lucen
dc.contributor.authorMarder, Seth Ren
dc.contributor.authorAl-Sayah, Mohammad H.en
dc.contributor.authorKaafarani, Bilal Ren
dc.date.accessioned2015-05-03T14:18:20Zen
dc.date.available2015-05-03T14:18:20Zen
dc.date.issued2015-04-27en
dc.identifier.citationDithieno[3,2-a:2',3'-c]phenazine-based Chemical Probe for Anions: A Spectroscopic Study of Binding 2015 RSC Adv.en
dc.identifier.issn2046-2069en
dc.identifier.doi10.1039/C5RA01416Fen
dc.identifier.urihttp://hdl.handle.net/10754/552106en
dc.description.abstractThe synthesis of a new anion-responsive molecule N,N'-(2,5-bis(4-(tert-butyl)phenyl)dithieno[3,2-a:2',3'-c]phenazine-9,10-diyl)bis(4-methylbenzenesulfonamide) (1) is reported. The sensitivities of the spectroscopic properties of 1 in the presence of various anions were examined using UV-vis absorption spectroscopy, fluorescence and 1H NMR titration experiments. Strong binding of 1 to carboxylate, cyanide, fluoride and dihydrogen phosphate anions results in an increase in quantum yield for emission of 1, and changes in its 1H NMR chemical shifts. A significant electrostatic interaction of the tetrabutylammonium cation with 1, upon strong binding with the counter anion, was also indicated by the chemical shifts observed in the 1H NMR titrations. Binding constants of 1 to anions are also calculated based on the binding isotherms derived from NMR and UV-Vis titrations. DFT calculations show that the anion does not significantly impact the HOMO/LUMO levels (and subsequently the S0 -> S1 transition), but rather changes the strength of the S0 -> S2 transition, which accounts for the observed changes in the UV-vis spectra.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2015/RA/C5RA01416Fen
dc.rightsArchived with thanks to RSC Adv.en
dc.titleDithieno[3,2-a:2',3'-c]phenazine-based Chemical Probe for Anions: A Spectroscopic Study of Bindingen
dc.typeArticleen
dc.contributor.departmentSolar and Photovoltaic Engineering Research Centeren
dc.identifier.journalRSC Adv.en
dc.eprint.versionPost-printen
dc.contributor.institutionDepartment of Chemistry, American University of Bei rut, Beirut 1107-2020, Lebanonen
dc.contributor.institutionSchool of Chemistry & Biochemistry and Center for O rganic Photonics and Electronics, Georgia Institute of Technology, Atlanta, GA 30332-0400, USAen
dc.contributor.institutionDepartment of Biology, Chemistry and Environmental Sciences, American University of Sharjah, POB 26666, Sharjah, United Arab Emiratesen
kaust.authorBredas, Jean-Lucen
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