Dual fluorescence and excited-state structural relaxations in donor-acceptor stilbenes

Dina Pines; Ehud Pines; Wolfgang Rettig

doi:10.1021/jp013171e

Dual fluorescence and excited-state structural relaxations in donor-acceptor stilbenes

Dina Pines, Ehud Pines, Wolfgang Rettig

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

71 Scopus citations

Abstract

The time-resolved fluorescence behavior of two derivatives of 4-(dimethylamino)-4′-cyanostilbene (DCS) bearing a more voluminous (JCS) and less voluminous anilino group (ACS) was investigated in ethanol by reconstructing the emission spectra using picosecond time-resolved single-photon-counting technique. For JCS, these spectra exhibit a temporary isosbestic point, a clear indication of level dynamics between two emitting excited singlet states (LE and CT). Kinetic evaluation yielded a precursor-successor relationship between LE and CT and CT formation time constants of 4 ps for ACS and 8 ps for JCS. This slowing of the reaction for the compound with the larger volume of the donor moiety supports the assumption of a twisting mechanism being a major component of the reaction coordinate. An additional transient red shift of the CT band is observed for both compounds and follows the relatively slow solvation dynamics (ethanol).

Original language	English
Pages (from-to)	236-242
Number of pages	7
Journal	Journal of Physical Chemistry A
Volume	107
Issue number	2
DOIs	https://doi.org/10.1021/jp013171e
State	Published - 16 Jan 2003

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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title = "Dual fluorescence and excited-state structural relaxations in donor-acceptor stilbenes",

abstract = "The time-resolved fluorescence behavior of two derivatives of 4-(dimethylamino)-4′-cyanostilbene (DCS) bearing a more voluminous (JCS) and less voluminous anilino group (ACS) was investigated in ethanol by reconstructing the emission spectra using picosecond time-resolved single-photon-counting technique. For JCS, these spectra exhibit a temporary isosbestic point, a clear indication of level dynamics between two emitting excited singlet states (LE and CT). Kinetic evaluation yielded a precursor-successor relationship between LE and CT and CT formation time constants of 4 ps for ACS and 8 ps for JCS. This slowing of the reaction for the compound with the larger volume of the donor moiety supports the assumption of a twisting mechanism being a major component of the reaction coordinate. An additional transient red shift of the CT band is observed for both compounds and follows the relatively slow solvation dynamics (ethanol).",

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T1 - Dual fluorescence and excited-state structural relaxations in donor-acceptor stilbenes

AU - Pines, Dina

AU - Pines, Ehud

AU - Rettig, Wolfgang

PY - 2003/1/16

Y1 - 2003/1/16

N2 - The time-resolved fluorescence behavior of two derivatives of 4-(dimethylamino)-4′-cyanostilbene (DCS) bearing a more voluminous (JCS) and less voluminous anilino group (ACS) was investigated in ethanol by reconstructing the emission spectra using picosecond time-resolved single-photon-counting technique. For JCS, these spectra exhibit a temporary isosbestic point, a clear indication of level dynamics between two emitting excited singlet states (LE and CT). Kinetic evaluation yielded a precursor-successor relationship between LE and CT and CT formation time constants of 4 ps for ACS and 8 ps for JCS. This slowing of the reaction for the compound with the larger volume of the donor moiety supports the assumption of a twisting mechanism being a major component of the reaction coordinate. An additional transient red shift of the CT band is observed for both compounds and follows the relatively slow solvation dynamics (ethanol).

AB - The time-resolved fluorescence behavior of two derivatives of 4-(dimethylamino)-4′-cyanostilbene (DCS) bearing a more voluminous (JCS) and less voluminous anilino group (ACS) was investigated in ethanol by reconstructing the emission spectra using picosecond time-resolved single-photon-counting technique. For JCS, these spectra exhibit a temporary isosbestic point, a clear indication of level dynamics between two emitting excited singlet states (LE and CT). Kinetic evaluation yielded a precursor-successor relationship between LE and CT and CT formation time constants of 4 ps for ACS and 8 ps for JCS. This slowing of the reaction for the compound with the larger volume of the donor moiety supports the assumption of a twisting mechanism being a major component of the reaction coordinate. An additional transient red shift of the CT band is observed for both compounds and follows the relatively slow solvation dynamics (ethanol).

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Dual fluorescence and excited-state structural relaxations in donor-acceptor stilbenes

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