Property Tuning in <i>N</i> ‐Methylpyrrole Azo‐Photoswitches via Modification of the Peripheral Substituents
Differently substituted pyrrole-azo-benzene molecular photoswitches were prepared in a straightforward synthetic way. Their fundamental properties were investigated by XRD analysis, differential scanning calorimetry, thermogravimetric analysis, cyclic voltammetry, UV-Vis absorption spectroscopy, Hyper-Rayleigh Scattering, and NMR spectroscopy; the experimental results were further corroborated by DFT calculations. Thermal robustness, the HOMO/LUMO levels, and the absorption properties were altered mostly by substituting the N-methylpyrrole moiety and further fine-tuned by modifying the benzene substituents. The pyrrole substituent also proved crucial for the second-order non-linear optical (NLO) response as well as the photoswitching performance. Both fast and slow molecular switches can be designed with the half-life of the (Z) -isomer ranging from 48 seconds to 23.28 hours and the E/Z molar ratio up to 12/88. This comprehensive study allowed elucidation of the fundamental structure-property relationships and subsequently addresses the key aspects of the property tuning via substitution in molecular azo-photoswitches.
Authors
- Frédéric Castet (ORCID: https://orcid.org/0000-0002-6622-2402)
- Michaela Fecková (ORCID: https://orcid.org/0000-0001-6644-3590)
- Angela Dellai (ORCID: https://orcid.org/0000-0002-7366-5228)
- Patrik Pařík (ORCID: https://orcid.org/0000-0002-7434-3116)
- Milan Klikar (ORCID: https://orcid.org/0000-0002-7149-2116)
- Filip Bureš (ORCID: https://orcid.org/0000-0002-2832-6673)
- Jan Podlesný (ORCID: https://orcid.org/0000-0003-1592-8744)
- Zdeňka Růžičková (ORCID: https://orcid.org/0000-0003-0259-5557)
- Veronika Jelínková (ORCID: https://orcid.org/0000-0002-6897-2370)
- Martina Vachtlová (ORCID: https://orcid.org/0000-0002-2833-1528)
- Vincent Rodriguez (ORCID: https://orcid.org/0000-0001-6804-9757)
- Oldřich Pytela
- Matt Hugget
- Lauryne Verwaerde
- Bixente Sempé
Institutions
- Centre National de la Recherche Scientifique (FR)
- University of Pardubice (CZ)
- Université de Bordeaux (FR)
- Institut des Sciences Moléculaires (FR)
- Institute of Technology and Business (CZ)
- Institut Polytechnique de Bordeaux (FR)
Publication Details
- Journal
- Chemistry - A European Journal
- Published
- 2024-12-28
- DOI
- https://doi.org/10.1002/chem.202404221
- Citations
- 4
- Primary Topic
- Photochromic and Fluorescence Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.47
Funders
- Technology Agency of the Czech Republic
- Agence Nationale de la Recherche
- Ministerstvo Školství, Mládeže a Tělovýchovy
- Université de Bordeaux
- Université de Pau et des Pays de l'Adour