Publication result detail

Photoswitchable hydrazones with pyridine-based rotors and halogen substituents

KOTÁSKOVÁ, L.; JEWULA, P.; HERCHEL, R.; NEMEC, I.; NEUGEBAUER, P.

Original Title

Photoswitchable hydrazones with pyridine-based rotors and halogen substituents

English Title

Photoswitchable hydrazones with pyridine-based rotors and halogen substituents

Type

WoS Article

Original Abstract

The Z,E-photoisomerization of pyridine-based hydrazone switches is typically suppressed due to the presence of pyridine-based rotors. The crystal structures of studied compounds were investigated using theoretical methods combining DFT and QT-AIM calculations to unveil the nature and properties of the intramolecular hydrogen bonding. In this study, we introduced a new series of pyridine-based hydrazones anchored with o-halogen substituents (2-X) and investigated their photoswitching abilities using 1H NMR and UV-Vis spectroscopy. The efficiency of the photoisomerization from initial 2-X-Z to the 2-X-E isomer varied, with the highest yield observed for 2-Cl-E (55%). Our findings, supported by DFT calculations, revealed the formation of a new diastereomer, 2-X-E*, upon back-photoisomerization. We demonstrated that hydrazones from the 2-X series can be reversibly photoswitched using irradiation from the UV-Vis range, and additionally, we explored the effect of the halogen atom on their switching capabilities and also on their thermodynamics and kinetics of photoswitching, determining their molecular solar thermal energy storage potential. We report on the E,Z-photoisomerization of hydrazone switches with pyridine-based rotors and halogen-substituted stators.

English abstract

The Z,E-photoisomerization of pyridine-based hydrazone switches is typically suppressed due to the presence of pyridine-based rotors. The crystal structures of studied compounds were investigated using theoretical methods combining DFT and QT-AIM calculations to unveil the nature and properties of the intramolecular hydrogen bonding. In this study, we introduced a new series of pyridine-based hydrazones anchored with o-halogen substituents (2-X) and investigated their photoswitching abilities using 1H NMR and UV-Vis spectroscopy. The efficiency of the photoisomerization from initial 2-X-Z to the 2-X-E isomer varied, with the highest yield observed for 2-Cl-E (55%). Our findings, supported by DFT calculations, revealed the formation of a new diastereomer, 2-X-E*, upon back-photoisomerization. We demonstrated that hydrazones from the 2-X series can be reversibly photoswitched using irradiation from the UV-Vis range, and additionally, we explored the effect of the halogen atom on their switching capabilities and also on their thermodynamics and kinetics of photoswitching, determining their molecular solar thermal energy storage potential. We report on the E,Z-photoisomerization of hydrazone switches with pyridine-based rotors and halogen-substituted stators.

Keywords

ISOMERIZATION MECHANISM; BASIS-SETS; CRYSTAL; PH

Key words in English

ISOMERIZATION MECHANISM; BASIS-SETS; CRYSTAL; PH

Authors

KOTÁSKOVÁ, L.; JEWULA, P.; HERCHEL, R.; NEMEC, I.; NEUGEBAUER, P.

RIV year

2025

Released

27.06.2024

Publisher

ROYAL SOC CHEMISTRY

Location

CAMBRIDGE

ISBN

2046-2069

Periodical

RSC Advances

Volume

14

Number

29

State

United Kingdom of Great Britain and Northern Ireland

Pages from

20856

Pages to

20866

Pages count

11

URL

https://pubs.rsc.org/en/content/articlelanding/2024/ra/d4ra02909g

Full text in the Digital Library

http://hdl.handle.net/11012/249998

BibTex

@article{BUT190011,
  author="Lucie {Kotásková} and Pawel {Jewula} and Radovan {Herchel} and Ivan {Nemec} and Petr {Neugebauer}",
  title="Photoswitchable hydrazones with pyridine-based rotors and halogen substituents",
  journal="RSC Advances",
  year="2024",
  volume="14",
  number="29",
  pages="20856--20866",
  doi="10.1039/d4ra02909g",
  url="https://pubs.rsc.org/en/content/articlelanding/2024/ra/d4ra02909g"
}

Documents

d4ra02909g