Azomethine phthalimides fluorescent E -> Z photoswitches
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216305%3A26310%2F20%3APU139542" target="_blank" >RIV/00216305:26310/20:PU139542 - isvavai.cz</a>
Result on the web
<a href="https://www.sciencedirect.com/science/article/abs/pii/S1010603020302422" target="_blank" >https://www.sciencedirect.com/science/article/abs/pii/S1010603020302422</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1016/j.jphotochem.2020.112443" target="_blank" >10.1016/j.jphotochem.2020.112443</a>
Alternative languages
Result language
angličtina
Original language name
Azomethine phthalimides fluorescent E -> Z photoswitches
Original language description
Herein, we report the synthesis and E -> Z photoswitching behavior of two 4-substituted azomethine phthalimides containing anthracenyl and 4-(dimethylamino)phenyl moieties (EAMP1 and EAMP2). These compounds represent newly synthesized and unstudied photoswitches with dual fluorescence properties as E-isomers and at photostationary state (PSS) depending on the solvent polarity. Steady-state fluorescence measurements were performed in various solvents and the results show strong sensitivity on the environmental polarity. The kinetics of E -> Z photoswitching to PSS was studied in AcCN by visible light activation at 410 nm (EAMP1) and long wavelength UV-light activation at 350 nm (EAMP2). The quantitative and qualitative performance of the switching behavior was evaluated by the degree of photoisomerization (R) and the rate constant (k). It was found for EAMP1 R = 6.95 %, k = 8.87 x 10(-4) s(-1) and EAMP2 R = 88.72 %, k = 4.00 x 10(-4) s(-1), respectively. The reason for the lower photoconversion of EAMP1 compared to the EAMP2 was analyzed through optimization of the molecular geometry of E- and Z-isomers in the ground state (S-0) and first excited state (S-1) by DFT/TD-DFT calculations with B3LYP/6-31 + G(d,p) level of theory using IEFPCM in AcCN. It was found that Eisomers in the S-0 have nonplanar conformation, while the Z-isomer of EAMP1 prefers twisted conformation and the Z-isomer of EAMP2 T-shaped conformation is energetically advantageous compared to the twisted one. The reason is the weak H.....pi noncovalent interaction (NCI) between 4-(dimethylamino)phenyl moiety and phthalimide ring. Moreover, the Z-isomer of EAMP2 is unusual stable up to 600 min at room temperature in dark compared to the EAMP1, which undergoes full Z -> E relaxation for less than 60 min at the same conditions. The Z -> E relaxation of EAMP2 is achieved for 90 min at 60 degrees C. The fluorescence E -> Z switching behavior was studied by emission measurements in AcCN and 1,4-DOX as E-isome
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA19-22783S" target="_blank" >GA19-22783S: Molecular energy harvesting materials: towards breaking the limits</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Photochemistry and Photobiology A:Chemistry
ISSN
1010-6030
e-ISSN
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Volume of the periodical
393
Issue of the periodical within the volume
112443
Country of publishing house
CH - SWITZERLAND
Number of pages
14
Pages from-to
1-14
UT code for WoS article
000528279200010
EID of the result in the Scopus database
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