Visible Light Switching of Ortho-Functionalized Azo Phthalimides with Tunable Z-Isomer Stability

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Visible Light Switching of Ortho-Functionalized Azo Phthalimides with Tunable Z-Isomer Stability

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Visible Light Switching of Ortho-Functionalized Azo Phthalimides with Tunable Z-Isomer Stability

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

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OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA24-10479S" target="_blank" >GA24-10479S: Molekulární krystaly s blízkou infračervenou emisí pro zobrazování nové generace (Crystal-NIR)</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

The Journal of Organic Chemistry

ISSN

0022-3263

e-ISSN

1520-6904

Svazek periodika

37

Číslo periodika v rámci svazku

90

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

12904-12915

Kód UT WoS článku

001568265000001

EID výsledku v databázi Scopus

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