Fluorination effects on photoisomerization dynamics of azobenzene

被引：0

作者：

Kim, Youngoh ^{[1
,2
]}

Choi, Joonmyung ^{[1
,2
]}

机构：

[1] Department of Mechanical Design Engineering, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul

[2] Department of Mechanical Engineering, BK21 FOUR ERICA-ACE Center, Hanyang University, 55 Hanyangdaehak-ro, Sangnok-gu, Ansan

来源：

Journal of Molecular Liquids | 2024年 / 415卷

基金：

新加坡国家研究基金会;

关键词：

Azobenzene; Electron-withdrawing group; Photoisomerization; Photomechanics;

D O I：

10.1016/j.molliq.2024.126345

中图分类号：

学科分类号：

摘要：

The photoisomerization dynamics of azobenzene (Azo-H) and its modulation by electron-withdrawing groups (EWGs) are important for designing photophysical applications, such as artificial muscles, liquid crystal displays, and solar thermal fuels. In this study, the electron-withdrawal kinetics of fluorination and the tailoring of the photoisomerization dynamics of azobenzene were explored using theoretical multiscale simulations. First-principle calculations provide insight into the mechanical aspects of photoisomerization, whereas molecular dynamics simulations offer a time-dependent perspective. Fluorinated azobenzene (Azo-F) exhibits superior photoisomerization responsiveness owing to changes in its molecular conformation and energy states induced by the EWG. These thermodynamic advantages were influenced by the stabilization of the molecular orbitals near the diazene groups. Despite the thermodynamic advantages of Azo-F, heavy fluorine atoms reduce the actuating force and work capacity owing to their increased inertia. This study provides a comprehensive understanding of photoisomerization kinetics modulated by the local fluorination of Azo-H. © 2024 Elsevier B.V.

引用

共 41 条

[1]

Bandara H.M.D., Burdette S.C., Photoisomerization in different classes of azobenzene, Chem. Soc. Rev., 41, pp. 1809-1825, (2012)

[2]

Koshima H., Ojima N., Uchimoto H., Mechanical Motion of Azobenzene Crystals upon Photoirradiation, J. Am. Chem. Soc., 131, pp. 6890-6891, (2009)

[3]

Briceno-Ahumada Z., Tapia-Burgos J.A., Diaz-Leyva P., Cadena-Aguilar A., Garcia-Hernandez F., Kozina A., Synthesis and cis-trans kinetics of an azobenzene-based molecular switch for light-responsive silica surfaces, J. Mol. Liq., 390, (2023)

[4]

Vapaavuori J., Bazuin C.G., Priimagi A., Supramolecular design principles for efficient photoresponsive polymer–azobenzene complexes, J. Mater. Chem. C, 6, pp. 2168-2188, (2018)

[5]

Shivanna J.M., Alaasar M., Hegde G., Azobenzene-based polycatenars: Investigation on photo switching properties and optical storage devices, J. Mol. Liq., 341, (2021)

[6]

Siewertsen R., Neumann H., Buchheim-Stehn B., Herges R., Nather C., Renth F., Temps F., Highly Efficient Reversible Z−E Photoisomerization of a Bridged Azobenzene with Visible Light through Resolved S1(nπ*) Absorption Bands, J. Am. Chem. Soc., 131, 43, pp. 15594-15595, (2009)

[7]

Bleger D., Schwarz J., Brouwer A.M., Hecht S., o–Fluoroazobenzenes as Readily Synthesized Photoswitches Offering Nearly Quantitative Two-Way Isomerization with Visible Light, J. Am. Chem. Soc., 134, pp. 20597-20600, (2012)

[8]

Gupta M., Ashy, Solar Thermal Energy Storage Systems Based on Discotic Nematic Liquid Crystals That Can Efficiently Charge and Discharge below 0 °C, Adv. Energy Mater., 14, (2024)

[9]

Kim Y., Choi J., Pseudo-catalytic kinetics induced by electron withdrawal of Na ions for cellulose activation: A theoretical multiscale study, Fuel, 364, (2024)

[10]

Kim Y., Choi J., Electromechanical origin of phonon dynamics exhibiting tunable anisotropic heat transport in layered nanostructures, Small Methods, 8, (2024)

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