Visible Light Switching of Ortho-Functionalized Azo Phthalimides with Tunable Z-Isomer Stability
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216305%3A26310%2F26%3A0200193" target="_blank" >RIV/00216305:26310/26:0200193 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/10.1021/acs.joc.5c01018?src=getftr&utm_source=clarivate&getft_integrator=clarivate" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.joc.5c01018?src=getftr&utm_source=clarivate&getft_integrator=clarivate</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.joc.5c01018" target="_blank" >10.1021/acs.joc.5c01018</a>
Alternative languages
Result language
angličtina
Original language name
Visible Light Switching of Ortho-Functionalized Azo Phthalimides with Tunable Z-Isomer Stability
Original language description
Herein, a novel class of azo photoswitches based on a phthalimide with an ortho azo bond to the imide ring is presented, exhibiting reversible isomerization under a broad range of visible light irradiation from 405 to 530 nm. Structural variations with heteroaryl or aryl segments attached to the 3-phthalylazo unit exhibit distinct spectral features, such as red-shifted absorption, well-separated absorption bands, and tunable stability of the metastable Z isomer, ranging from seconds to days. They differ drastically in the half-life of Z-isomer stability, ranging from several seconds (N-methylpyrrole) to days (N-methylimidazole). The ortho-cyanophenyl azo dye shows an n-pi* band separation of 22 nm between the E and Z isomers, enabling on-off switching by green (530 nm) and blue (430 nm) light. X-ray structural analysis reveals that the E isomer adopts a planar geometry. The Z isomers exhibit a T-shaped configuration for dyes with heteroaryl segments, while aryl Z isomers adopt a twisted conformation. Ground-state density functional theory calculations suggest a different mechanism for Z/E thermal relaxation depending on the heteroaryl or aryl substituents, explaining the varying stability of the Z isomers. Van't Hoff analysis of the thermal Z/E isomerization provided enthalpic and Gibbs free energy changes, supporting the substituent-dependent trends in Z-isomer stability.
Czech name
—
Czech description
—
Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10401 - Organic chemistry
Result continuities
Project
<a href="/en/project/GA24-10479S" target="_blank" >GA24-10479S: Near-infrared emitting molecular crystals for next generation imaging (Crystal-NIR)</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
The Journal of Organic Chemistry
ISSN
0022-3263
e-ISSN
1520-6904
Volume of the periodical
37
Issue of the periodical within the volume
90
Country of publishing house
US - UNITED STATES
Number of pages
12
Pages from-to
12904-12915
UT code for WoS article
001568265000001
EID of the result in the Scopus database
—