Femtosecond pump-probe measurements of solvation by hydrogen-bonding interactions

Ehud Pines; Dina Pines; Ying Zhong Ma; Graham R. Fleming

doi:10.1002/cphc.200301004

Femtosecond pump-probe measurements of solvation by hydrogen-bonding interactions

Ehud Pines, Dina Pines, Ying Zhong Ma, Graham R. Fleming

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

85 Scopus citations

Abstract

An additional ultrafast blue shift in the transient absorption spectra of hydrogen-bonding complexes of a strong photoacid, 8-hydroxypyrene 1,3,6-trisdimethylsulfonamide (HPTA), over the salvation response of the uncomplexed HPTA and also over that of the methoxy derivative of the photoacid (MPTA) in the presence of the hydrogen-bonding base was observed on optical excitation of the photoacid. The additional 55 ± 10 fs solvation response was found to be about 35% and 19% of the total C(t) of HPTA in dichloromethane (DCM) when it was hydrogen-bonded to dimethylsulfoxide (DMSO) and dioxane, respectively, and about 29% of the total C(t) of HPTA in dichloroethane (DCE) when it was hydrogen-bonded to DMSO. We have assigned this additional dynamic spectral shift to a transient change in the hydrogen bond (O-H⋯O) that links HPTA to the complexing base, after the electronic excitation of the photoacid.

Original language	English
Pages (from-to)	1315-1327
Number of pages	13
Journal	ChemPhysChem
Volume	5
Issue number	9
DOIs	https://doi.org/10.1002/cphc.200301004
State	Published - Sep 20 2004
Externally published	Yes

Keywords

Femtochemistry
Hydrogen-bonding interactions
Photoacids
Pump-probe spectroscopy
Solvation dynamics

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10.1002/cphc.200301004

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title = "Femtosecond pump-probe measurements of solvation by hydrogen-bonding interactions",

abstract = "An additional ultrafast blue shift in the transient absorption spectra of hydrogen-bonding complexes of a strong photoacid, 8-hydroxypyrene 1,3,6-trisdimethylsulfonamide (HPTA), over the salvation response of the uncomplexed HPTA and also over that of the methoxy derivative of the photoacid (MPTA) in the presence of the hydrogen-bonding base was observed on optical excitation of the photoacid. The additional 55 ± 10 fs solvation response was found to be about 35% and 19% of the total C(t) of HPTA in dichloromethane (DCM) when it was hydrogen-bonded to dimethylsulfoxide (DMSO) and dioxane, respectively, and about 29% of the total C(t) of HPTA in dichloroethane (DCE) when it was hydrogen-bonded to DMSO. We have assigned this additional dynamic spectral shift to a transient change in the hydrogen bond (O-H⋯O) that links HPTA to the complexing base, after the electronic excitation of the photoacid.",

keywords = "Femtochemistry, Hydrogen-bonding interactions, Photoacids, Pump-probe spectroscopy, Solvation dynamics",

author = "Ehud Pines and Dina Pines and Ma, {Ying Zhong} and Fleming, {Graham R.}",

year = "2004",

month = sep,

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doi = "10.1002/cphc.200301004",

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T1 - Femtosecond pump-probe measurements of solvation by hydrogen-bonding interactions

AU - Pines, Ehud

AU - Pines, Dina

AU - Ma, Ying Zhong

AU - Fleming, Graham R.

PY - 2004/9/20

Y1 - 2004/9/20

N2 - An additional ultrafast blue shift in the transient absorption spectra of hydrogen-bonding complexes of a strong photoacid, 8-hydroxypyrene 1,3,6-trisdimethylsulfonamide (HPTA), over the salvation response of the uncomplexed HPTA and also over that of the methoxy derivative of the photoacid (MPTA) in the presence of the hydrogen-bonding base was observed on optical excitation of the photoacid. The additional 55 ± 10 fs solvation response was found to be about 35% and 19% of the total C(t) of HPTA in dichloromethane (DCM) when it was hydrogen-bonded to dimethylsulfoxide (DMSO) and dioxane, respectively, and about 29% of the total C(t) of HPTA in dichloroethane (DCE) when it was hydrogen-bonded to DMSO. We have assigned this additional dynamic spectral shift to a transient change in the hydrogen bond (O-H⋯O) that links HPTA to the complexing base, after the electronic excitation of the photoacid.

AB - An additional ultrafast blue shift in the transient absorption spectra of hydrogen-bonding complexes of a strong photoacid, 8-hydroxypyrene 1,3,6-trisdimethylsulfonamide (HPTA), over the salvation response of the uncomplexed HPTA and also over that of the methoxy derivative of the photoacid (MPTA) in the presence of the hydrogen-bonding base was observed on optical excitation of the photoacid. The additional 55 ± 10 fs solvation response was found to be about 35% and 19% of the total C(t) of HPTA in dichloromethane (DCM) when it was hydrogen-bonded to dimethylsulfoxide (DMSO) and dioxane, respectively, and about 29% of the total C(t) of HPTA in dichloroethane (DCE) when it was hydrogen-bonded to DMSO. We have assigned this additional dynamic spectral shift to a transient change in the hydrogen bond (O-H⋯O) that links HPTA to the complexing base, after the electronic excitation of the photoacid.

KW - Femtochemistry

KW - Hydrogen-bonding interactions

KW - Photoacids

KW - Pump-probe spectroscopy

KW - Solvation dynamics

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U2 - 10.1002/cphc.200301004

DO - 10.1002/cphc.200301004

M3 - Article

AN - SCOPUS:5044239746

SN - 1439-4235

VL - 5

SP - 1315

EP - 1327

JO - ChemPhysChem

JF - ChemPhysChem

IS - 9

ER -

Femtosecond pump-probe measurements of solvation by hydrogen-bonding interactions

Abstract

Keywords

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