Design of High-Performance Pyridine/Quinoline Hydrazone Photoswitches.

Autor:	Mravec B; Department of Organic Chemistry, Faculty of Natural Sciences, Comenius University, Ilkovičova 6, 84215 Bratislava, Slovakia., Budzák Š; Department of Chemistry, Faculty of Natural Sciences, Matej Bel University, Tajovského 40, 97400 Banská Bystrica, Slovakia., Medved' M; Department of Chemistry, Faculty of Natural Sciences, Matej Bel University, Tajovského 40, 97400 Banská Bystrica, Slovakia.; Regional Centre of Advanced Technologies and Materials, Czech Advanced Technology and Research Institute (CATRIN), Palacký University Olomouc, Křížkovského 8, 77900 Olomouc, Czech Republic., Pašteka LF; Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University, Ilkovičova 6, 84215 Bratislava, Slovakia., Slavov C; Institute of Physical and Theoretical Chemistry, Faculty of Biochemistry, Chemistry, Pharmacy, Goethe University, Max-von-Laue-Str. 7, 60438 Frankfurt am Main, Germany., Saßmannshausen T; Institute of Physical and Theoretical Chemistry, Faculty of Biochemistry, Chemistry, Pharmacy, Goethe University, Max-von-Laue-Str. 7, 60438 Frankfurt am Main, Germany., Wachtveitl J; Institute of Physical and Theoretical Chemistry, Faculty of Biochemistry, Chemistry, Pharmacy, Goethe University, Max-von-Laue-Str. 7, 60438 Frankfurt am Main, Germany., Kožíšek J; Department of Physical Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, 81237 Bratislava, Slovakia., Hegedüsová L; Department of Organic Chemistry, Faculty of Natural Sciences, Comenius University, Ilkovičova 6, 84215 Bratislava, Slovakia., Filo J; Department of Organic Chemistry, Faculty of Natural Sciences, Comenius University, Ilkovičova 6, 84215 Bratislava, Slovakia., Cigáň M; Department of Organic Chemistry, Faculty of Natural Sciences, Comenius University, Ilkovičova 6, 84215 Bratislava, Slovakia.
Jazyk:	angličtina
Zdroj:	The Journal of organic chemistry [J Org Chem] 2021 Sep 03; Vol. 86 (17), pp. 11633-11646. Date of Electronic Publication: 2021 Jul 29.
DOI:	10.1021/acs.joc.1c01174
Abstrakt:	The design of P-type photoswitches with thermal stability of the metastable form of hundreds of years that would efficiently transform using excitation wavelengths above 350 nm remains a challenge in the field of photochromism. In this regard, we designed and synthesized an extended set of 13 pyridine/quinoline hydrazones and systematically investigated the structure-property relationships, defining their kinetic and photoswitching parameters. We show that the operational wavelengths of the pyridine hydrazone structural motif can be effectively shifted toward the visible region without simultaneous loss of their high thermal stability. Furthermore, we characterized the ground-state and excited-state potential energy surfaces with quantum-chemical calculations and ultrafast transient absorption spectroscopy, which allowed us to rationalize both the thermal and photochemical reaction mechanisms of the designed hydrazones. Whereas introducing an electron-withdrawing pyridyl moiety in benzoylpyridine hydrazones leads to thermal stabilities exceeding 200 years, extended π-conjugation in naphthoylquinoline hydrazones pushes the absorption maxima toward the visible spectral region. In either case, the compounds retain highly efficient photoswitching characteristics. Our findings open a route to the rational design of a new family of hydrazone-based P-type photoswitches with high application potential in photonics or photopharmacology.
Databáze:	MEDLINE
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