Novel Nitroxide-Substituted Hydrazone Switch: Experimental and Theoretical Insights into Photoswitching Behavior

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216305%3A26620%2F26%3A0199773" target="_blank" >RIV/00216305:26620/26:0199773 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/pdf/10.1021/acsorginorgau.5c00068?utm_source=clarivate&getft_integrator=clarivate" target="_blank" >https://pubs.acs.org/doi/pdf/10.1021/acsorginorgau.5c00068?utm_source=clarivate&getft_integrator=clarivate</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acsorginorgau.5c00068" target="_blank" >10.1021/acsorginorgau.5c00068</a>

Result language
angličtina
Original language name
Novel Nitroxide-Substituted Hydrazone Switch: Experimental and Theoretical Insights into Photoswitching Behavior
Original language description
Hydrazones are a versatile class of molecular switches with dual responsiveness to both light and pH. To investigate their switching properties, we incorporated a nitroxide moiety, enabling analysis by not only conventional techniques such as H-1 NMR and UV-vis spectroscopy but also EPR spectroscopy, which provides valuable insights into structure and dynamics. A novel nitroxide-substituted hydrazone switch (2) was synthesized and fully characterized. However, initial experiments using H-1 NMR and UV-vis revealed restricted photoisomerization of 2. Theoretical studies employing DFT and TD-DFT methods revealed the presence of the D-1 excited state related to pi -> pi* electron transfer of the nitroxide moiety, and D-2 excited state related to pi -> pi* electron transfer within the hydrazone moiety. The latter excitation results in weakening of the C=N bond and enables the rotation around the hydrazone bond; however, the internal conversion D-2 -> D-1 process is most likely responsible for the quenching of photoisomerization in 2. Additionally, pH-induced switching was monitored using UV-vis and EPR spectroscopy, revealing that strong acids such as trifluoroacetic acid had no significant effect on the paramagnetic center.
Czech name
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Czech description
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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
10401 - Organic chemistry

Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year
2026
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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