Solvent-Dependent Dual Fluorescence of the Push-Pull System 2-Diethylamino-7-Nitrofluorene

Handle URI:
http://hdl.handle.net/10754/627067
Title:
Solvent-Dependent Dual Fluorescence of the Push-Pull System 2-Diethylamino-7-Nitrofluorene
Authors:
Larsen, Martin A. B.; Stephansen, Anne B.; Alarousu, Erkki; Pittelkow, Michael; Mohammed, Omar F. ( 0000-0001-8500-1130 ) ; Sølling, Theis I
Abstract:
The solvent-dependent excited state behavior of the molecular push-pull system 2-diethylamino-7-nitrofluorene has been explored using femtosecond transient absorption spectroscopy in combination with density functional theory calculations. Several excited state minima have been identified computationally, all possessing significant intramolecular charge transfer character. The experimentally observed dual fluorescence is suggested to arise from a planar excited state minimum and another minimum reached by twisting of the aryl-nitrogen bond of the amino group. The majority of the excited state population, however, undergo non-radiative transitions and potential excited deactivation pathways are assessed in the computational investigation. A third excited state conformer, characterized by twisting around the aryl-nitrogen bond of the nitro group, is reasoned to be responsible for the majority of the non-radiative decays and a crossing between the excited state and ground state is localized. Additionally, ultrafast intersystem crossing is observed in the apolar solvent cyclohexane and rationalized to occur via an El-Sayed assisted transition from one of the identified excited state minima. The solvent thus determines more than just the fluorescence lifetime and shapes the potential energy landscape, thereby dictating the available excited state pathways.
KAUST Department:
KAUST Solar Center (KSC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Citation:
Larsen MAB, Stephansen AB, Alarousu E, Pittelkow M, Mohammed OF, et al. (2018) Solvent-Dependent Dual Fluorescence of the Push-Pull System 2-Diethylamino-7-Nitrofluorene. Physical Chemistry Chemical Physics. Available: http://dx.doi.org/10.1039/c8cp00235e.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Physical Chemistry Chemical Physics
Issue Date:
31-Jan-2018
DOI:
10.1039/c8cp00235e
Type:
Article
ISSN:
1463-9076; 1463-9084
Sponsors:
E.A. and O.F.M. gratefully acknowledge funding support from KAUST. Miss Sidsel A. Bogh and Dr. Martin Rosenberg are both thanked for their advice and suggestions in obtaining fluorescence spectra of the weakly fluorescent compounds.
Additional Links:
http://pubs.rsc.org/en/Content/ArticleLanding/2018/CP/C8CP00235E#!divAbstract
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Solar Center (KSC)

Full metadata record

DC FieldValue Language
dc.contributor.authorLarsen, Martin A. B.en
dc.contributor.authorStephansen, Anne B.en
dc.contributor.authorAlarousu, Erkkien
dc.contributor.authorPittelkow, Michaelen
dc.contributor.authorMohammed, Omar F.en
dc.contributor.authorSølling, Theis Ien
dc.date.accessioned2018-02-07T07:02:29Z-
dc.date.available2018-02-07T07:02:29Z-
dc.date.issued2018-01-31en
dc.identifier.citationLarsen MAB, Stephansen AB, Alarousu E, Pittelkow M, Mohammed OF, et al. (2018) Solvent-Dependent Dual Fluorescence of the Push-Pull System 2-Diethylamino-7-Nitrofluorene. Physical Chemistry Chemical Physics. Available: http://dx.doi.org/10.1039/c8cp00235e.en
dc.identifier.issn1463-9076en
dc.identifier.issn1463-9084en
dc.identifier.doi10.1039/c8cp00235een
dc.identifier.urihttp://hdl.handle.net/10754/627067-
dc.description.abstractThe solvent-dependent excited state behavior of the molecular push-pull system 2-diethylamino-7-nitrofluorene has been explored using femtosecond transient absorption spectroscopy in combination with density functional theory calculations. Several excited state minima have been identified computationally, all possessing significant intramolecular charge transfer character. The experimentally observed dual fluorescence is suggested to arise from a planar excited state minimum and another minimum reached by twisting of the aryl-nitrogen bond of the amino group. The majority of the excited state population, however, undergo non-radiative transitions and potential excited deactivation pathways are assessed in the computational investigation. A third excited state conformer, characterized by twisting around the aryl-nitrogen bond of the nitro group, is reasoned to be responsible for the majority of the non-radiative decays and a crossing between the excited state and ground state is localized. Additionally, ultrafast intersystem crossing is observed in the apolar solvent cyclohexane and rationalized to occur via an El-Sayed assisted transition from one of the identified excited state minima. The solvent thus determines more than just the fluorescence lifetime and shapes the potential energy landscape, thereby dictating the available excited state pathways.en
dc.description.sponsorshipE.A. and O.F.M. gratefully acknowledge funding support from KAUST. Miss Sidsel A. Bogh and Dr. Martin Rosenberg are both thanked for their advice and suggestions in obtaining fluorescence spectra of the weakly fluorescent compounds.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2018/CP/C8CP00235E#!divAbstracten
dc.rightsArchived with thanks to Physical Chemistry Chemical Physicsen
dc.titleSolvent-Dependent Dual Fluorescence of the Push-Pull System 2-Diethylamino-7-Nitrofluoreneen
dc.typeArticleen
dc.contributor.departmentKAUST Solar Center (KSC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalPhysical Chemistry Chemical Physicsen
dc.eprint.versionPost-printen
dc.contributor.institutionDepartment of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmarken
dc.contributor.institutionDepartment of Molecular Physics, Fritz-Haber Institute of the Max-Planck Society, Faradayweg 4–6, 14195 Berlin, Germanyen
kaust.authorAlarousu, Erkkien
kaust.authorMohammed, Omar F.en
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