Title :

The impact of dihedral angle in aryl groups on the photocyclization reactivity of inverse-type diarylethenes

Author(s) :

Suganuma, M. [Auteur]
Osaka Metropolitan University
Kitagawa, D. [Auteur]
Osaka Metropolitan University
Hamatani, S. [Auteur]
Osaka Metropolitan University
Sotome, H. [Auteur]
Osaka University [Osaka]
Mittelheisser, Cédric [Auteur]
Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 [LASIRE]
Sliwa, Michel [Auteur]
Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516
Ito, S. [Auteur]
Osaka University [Osaka]
Miyasaka, H. [Auteur]
Osaka University [Osaka]
Kobatake, S. [Auteur]
Osaka University [Osaka]

Journal title :

J. Mater. Chem. C

Abbreviated title :

J. Mater. Chem. C

Volume number :

-

Pages :

-

Publication date :

2025-02-15

ISSN :

2050-7526

HAL domain(s) :

Chimie/Chimie théorique et/ou physique

English abstract : [en]

Photoreactivity in crystals is one of the essential properties for creating photo-functional crystalline materials. This study explores the impact of the dihedral angle in aryl groups on the photocyclization reactivity of ...
Show more >Photoreactivity in crystals is one of the essential properties for creating photo-functional crystalline materials. This study explores the impact of the dihedral angle in aryl groups on the photocyclization reactivity of inverse-type diarylethenes, both in solution and crystalline phases. By synthesizing various diarylethene derivatives with different dihedral angles, the relationship between structural geometry and photoreactivity is systematically examined. We find that larger dihedral angles between the thiophene and phenyl rings enhance photocyclization reactivity in solution, indicating that destabilized π-conjugation lowers the activation barrier. In fact, ultrafast spectroscopy confirms that the cyclization time constant decreases with larger dihedral angles. In the crystalline phase, X-ray crystallographic analysis shows that all diarylethene derivatives adopt ideally photoreactive anti-parallel conformations, but only crystals with a dihedral angle exceeding approximately 81° exhibit photocyclization. These findings indicate that a certain threshold dihedral angle is essential for photocyclization to occur in crystals. The results of this work provide new insights into the role of molecular geometry in photoreactivity and offer a strategy for designing functional photochromic materials that operate efficiently in the solid state.Show less >

Language :

Anglais

Audience :

Internationale

Popular science :

Non

Administrative institution(s) :

Université de Lille
CNRS

Collections :

• Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516

Submission date :

2025-02-20T22:01:48Z
2025-02-28T09:24:55Z