Adiabatic Triplet State Tautomerization of
p-Hydroxyacetophenone in Aqueous Solution

J 2012

Adiabatic Triplet State Tautomerization of p-Hydroxyacetophenone in Aqueous Solution

KLÍČOVÁ, Ľubica, Peter ŠEBEJ, Tomáš ŠOLOMEK, Bruno HELLRUNG, Petr SLAVÍČEK et. al.

Basic information

Original name

Adiabatic Triplet State Tautomerization of p-Hydroxyacetophenone in Aqueous Solution

Authors

KLÍČOVÁ, Ľubica (203 Czech Republic, belonging to the institution), Peter ŠEBEJ (703 Slovakia, belonging to the institution), Tomáš ŠOLOMEK (703 Slovakia, belonging to the institution), Bruno HELLRUNG (756 Switzerland), Petr SLAVÍČEK (203 Czech Republic), Petr KLÁN (203 Czech Republic, guarantor, belonging to the institution), Dominik HEGER (203 Czech Republic, belonging to the institution) and Jakob WIRZ (756 Switzerland)

Edition

Journal of Physical Chemistry A, USA, The American Chemical Society, 2012, 1089-5639

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10401 Organic chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 2.771

RIV identification code

RIV/00216224:14310/12:00058036

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1021/jp3011469

UT WoS

000301766500040

Keywords in English

Photochemistry; p-Hydroxyacetophenone; Laser flash spectroscopy

Abstract

V originále

The primary photophysical processes of p-hydroxyacetophenone (HA) and the ensuing proton transfer reactions in aqueous solution were investigated by picosecond pump–probe spectroscopy and nanosecond laser flash photolysis. Previous studies have led to mutually inconsistent conclusions. The combined data allow us to rationalize the excited-state proton transfer processes of HA in terms of a comprehensive, well-established reaction scheme. Following fast and quantitative ISC to the triplet state, 3HA*, adiabatic proton transfer through solvent water simultaneously forms both the anion, 3A–*, and the quinoid triplet enol tautomer, 3Q*. The latter subsequently equilibrates with its anion 3A–*. Ionization and tautomerization are likely to compete with the desired release reactions of p-hydroxyphenacyl photoremovable protecting groups.

Links

ED0001/01/01, research and development project

Name: CETOCOEN

GA203/09/0748, research and development project

Name: Nové fotoaktivovatelné sloučeniny pro organickou chemii a biologii

Investor: Czech Science Foundation, New photoactivatable compounds for organic chemistry and biology

Citovat

KLÍČOVÁ, Ľubica, Peter ŠEBEJ, Tomáš ŠOLOMEK, Bruno HELLRUNG, Petr SLAVÍČEK, Petr KLÁN, Dominik HEGER and Jakob WIRZ. Adiabatic Triplet State Tautomerization of p-Hydroxyacetophenone in Aqueous Solution. Journal of Physical Chemistry A. USA: The American Chemical Society, 2012, vol. 116, No 11, p. 2935-2944. ISSN 1089-5639. Available from: https://dx.doi.org/10.1021/jp3011469.

@article{1081098,
   author = {Klíčová, Ľubica and Šebej, Peter and Šolomek, Tomáš and Hellrung, Bruno and Slavíček, Petr and Klán, Petr and Heger, Dominik and Wirz, Jakob},
   article_location = {USA},
   article_number = {11},
   doi = {http://dx.doi.org/10.1021/jp3011469},
   keywords = {Photochemistry; p-Hydroxyacetophenone; Laser flash spectroscopy},
   language = {eng},
   issn = {1089-5639},
   journal = {Journal of Physical Chemistry A},
   title = {Adiabatic Triplet State Tautomerization of p-Hydroxyacetophenone in Aqueous Solution},
   url = {http://pubs.acs.org/doi/abs/10.1021/jp3011469},
   volume = {116},
   year = {2012}
}

TY  - JOUR
ID  - 1081098
AU  - Klíčová, Ľubica - Šebej, Peter - Šolomek, Tomáš - Hellrung, Bruno - Slavíček, Petr - Klán, Petr - Heger, Dominik - Wirz, Jakob
PY  - 2012
TI  - Adiabatic Triplet State Tautomerization of p-Hydroxyacetophenone in Aqueous Solution
JF  - Journal of Physical Chemistry A
VL  - 116
IS  - 11
SP  - 2935-2944
EP  - 2935-2944
PB  - The American Chemical Society
SN  - 10895639
KW  - Photochemistry
KW  - p-Hydroxyacetophenone
KW  - Laser flash spectroscopy
UR  - http://pubs.acs.org/doi/abs/10.1021/jp3011469
N2  - The primary photophysical processes of p-hydroxyacetophenone (HA) and the ensuing proton transfer reactions in aqueous solution were investigated by picosecond pump–probe spectroscopy and nanosecond laser flash photolysis. Previous studies have led to mutually inconsistent conclusions. The combined data allow us to rationalize the excited-state proton transfer processes of HA in terms of a comprehensive, well-established reaction scheme. Following fast and quantitative ISC to the triplet state, 3HA*, adiabatic proton transfer through solvent water simultaneously forms both the anion, 3A–*, and the quinoid triplet enol tautomer, 3Q*. The latter subsequently equilibrates with its anion 3A–*. Ionization and tautomerization are likely to compete with the desired release reactions of p-hydroxyphenacyl photoremovable protecting groups.
ER  -

KLÍČOVÁ, Ľubica, Peter ŠEBEJ, Tomáš ŠOLOMEK, Bruno HELLRUNG, Petr SLAVÍČEK, Petr KLÁN, Dominik HEGER and Jakob WIRZ. Adiabatic Triplet State Tautomerization of p-Hydroxyacetophenone in Aqueous Solution. \textit{Journal of Physical Chemistry A}. USA: The American Chemical Society, 2012, vol.~116, No~11, p.~2935-2944. ISSN~1089-5639. Available from: https://dx.doi.org/10.1021/jp3011469.

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