The complex photochemistry of coumarin-3-carboxylic acid in
acetonitrile and methanol

J 2022

The complex photochemistry of coumarin-3-carboxylic acid in acetonitrile and methanol

YANG, Qiuyun, Jiri VANA and Petr KLÁN

Basic information

Original name

The complex photochemistry of coumarin-3-carboxylic acid in acetonitrile and methanol

Authors

YANG, Qiuyun (156 China, belonging to the institution), Jiri VANA and Petr KLÁN (203 Czech Republic, guarantor, belonging to the institution)

Edition

PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES, CAMBRIDGE, ROYAL SOC CHEMISTRY, 2022, 1474-905X

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10403 Physical chemistry

Country of publisher

United Kingdom of Great Britain and Northern Ireland

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 3.100

RIV identification code

RIV/00216224:14310/22:00126427

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1007/s43630-022-00238-8

UT WoS

000796316200001

Keywords in English

Photochemistry; Coumarin; Photooxidation; Singlet oxygen

Abstract

V originále

Irradiation of coumarin-3-carboxylic acid in acetonitrile and methanol solutions at 355 nm results in complex multistep photochemical transformations, strongly dependent on the solvent properties and oxygen content. A number of reaction intermediates, which themselves undergo further (photo)chemical reactions, were identified by steady-state and transient absorption spectroscopy, mass spectrometry, and NMR and product analyses. The triplet excited compound in acetonitrile undergoes decarboxylation to give a 3-coumarinyl radical that traps molecular oxygen to form 3-hydroxycoumarin as the major but chemically reactive intermediate. This compound is oxygenated by singlet oxygen, produced by coumarin-3-carboxylic acid sensitization, followed by a pyrone ring-opening reaction to give an oxalic acid derivative. The subsequent steps lead to the production of salicylaldehyde, carbon monoxide, and carbon dioxide as the final products. When 3-coumarinyl radical is not trapped by oxygen in degassed acetonitrile, it abstracts hydrogen from the solvent and undergoes triplet-sensitized [2 + 2] cycloaddition. The reaction of 3-coumarinyl radical with oxygen is largely suppressed in aerated methanol as a better H-atom donor, and coumarin is obtained as the primary product in good yields. Because coumarin derivatives are used in many photophysical and photochemical applications, this work provides detailed and sometimes surprising insights into their complex phototransformations.

Links

EF17_043/0009632, research and development project

Name: CETOCOEN Excellence

GA21-01799S, research and development project

Name: Flavonoidy jako unikátní třída molekul fotochemicky uvolňujících oxid uhelnatý

Investor: Czech Science Foundation

LM2018121, research and development project

Name: Výzkumná infrastruktura RECETOX (Acronym: RECETOX RI)

Investor: Ministry of Education, Youth and Sports of the CR, RECETOX RI

857560, interní kód MU
(CEP code: EF17_043/0009632)

Name: CETOCOEN Excellence (Acronym: CETOCOEN Excellence)

Investor: European Union, Spreading excellence and widening participation

Citovat

YANG, Qiuyun, Jiri VANA and Petr KLÁN. The complex photochemistry of coumarin-3-carboxylic acid in acetonitrile and methanol. PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES. CAMBRIDGE: ROYAL SOC CHEMISTRY, 2022, vol. 21, No 8, p. 1481-1495. ISSN 1474-905X. Available from: https://dx.doi.org/10.1007/s43630-022-00238-8.

@article{2211083,
   author = {Yang, Qiuyun and Vana, Jiri and Klán, Petr},
   article_location = {CAMBRIDGE},
   article_number = {8},
   doi = {http://dx.doi.org/10.1007/s43630-022-00238-8},
   keywords = {Photochemistry; Coumarin; Photooxidation; Singlet oxygen},
   language = {eng},
   issn = {1474-905X},
   journal = {PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES},
   title = {The complex photochemistry of coumarin-3-carboxylic acid in acetonitrile and methanol},
   url = {https://link.springer.com/article/10.1007/s43630-022-00238-8},
   volume = {21},
   year = {2022}
}

TY  - JOUR
ID  - 2211083
AU  - Yang, Qiuyun - Vana, Jiri - Klán, Petr
PY  - 2022
TI  - The complex photochemistry of coumarin-3-carboxylic acid in acetonitrile and methanol
JF  - PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES
VL  - 21
IS  - 8
SP  - 1481-1495
EP  - 1481-1495
PB  - ROYAL SOC CHEMISTRY
SN  - 1474905X
KW  - Photochemistry
KW  - Coumarin
KW  - Photooxidation
KW  - Singlet oxygen
UR  - https://link.springer.com/article/10.1007/s43630-022-00238-8
N2  - Irradiation of coumarin-3-carboxylic acid in acetonitrile and methanol solutions at 355 nm results in complex multistep photochemical transformations, strongly dependent on the solvent properties and oxygen content. A number of reaction intermediates, which themselves undergo further (photo)chemical reactions, were identified by steady-state and transient absorption spectroscopy, mass spectrometry, and NMR and product analyses. The triplet excited compound in acetonitrile undergoes decarboxylation to give a 3-coumarinyl radical that traps molecular oxygen to form 3-hydroxycoumarin as the major but chemically reactive intermediate. This compound is oxygenated by singlet oxygen, produced by coumarin-3-carboxylic acid sensitization, followed by a pyrone ring-opening reaction to give an oxalic acid derivative. The subsequent steps lead to the production of salicylaldehyde, carbon monoxide, and carbon dioxide as the final products. When 3-coumarinyl radical is not trapped by oxygen in degassed acetonitrile, it abstracts hydrogen from the solvent and undergoes triplet-sensitized [2 + 2] cycloaddition. The reaction of 3-coumarinyl radical with oxygen is largely suppressed in aerated methanol as a better H-atom donor, and coumarin is obtained as the primary product in good yields. Because coumarin derivatives are used in many photophysical and photochemical applications, this work provides detailed and sometimes surprising insights into their complex phototransformations.
ER  -

YANG, Qiuyun, Jiri VANA and Petr KLÁN. The complex photochemistry of coumarin-3-carboxylic acid in acetonitrile and methanol. \textit{PHOTOCHEMICAL \&{}amp; PHOTOBIOLOGICAL SCIENCES}. CAMBRIDGE: ROYAL SOC CHEMISTRY, 2022, vol.~21, No~8, p.~1481-1495. ISSN~1474-905X. Available from: https://dx.doi.org/10.1007/s43630-022-00238-8.

Detailed Information on Publication Record