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Columnar Aggregates of Azobenzene Stars: Exploring Intermolecular Interactions, Structure, and Stability in Atomistic Simulations
Article

Cyclic Photoisomerization of Azobenzene in Atomistic Simulations: Modeling the Effect of Light on Columnar Aggregates of Azo Stars

1
Institute Theory of Polymers, Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany
2
Dresden Center for Computational Materials Science (DCMS), Technische Universität Dresden, 01062 Dresden, Germany
*
Authors to whom correspondence should be addressed.
Academic Editors: Estelle Léonard and Muriel Billamboz
Molecules 2021, 26(24), 7674; https://doi.org/10.3390/molecules26247674
Received: 30 November 2021 / Revised: 14 December 2021 / Accepted: 15 December 2021 / Published: 18 December 2021
(This article belongs to the Special Issue Azobenzene and Applications: From Catalysis to Biology)
This computational study investigates the influence of light on supramolecular aggregates of three-arm azobenzene stars. Every star contains three azobenzene (azo) moieties, each able to undergo reversible photoisomerization. In solution, the azo stars build column-shaped supramolecular aggregates. Previous experimental works report severe morphological changes of these aggregates under UV–Vis light. However, the underlying molecular mechanisms are still debated. Here we aim to elucidate how light affects the structure and stability of the columnar stacks on the molecular scale. The system is investigated using fully atomistic molecular dynamics (MD) simulations. To implement the effects of light, we first developed a stochastic model of the cyclic photoisomerization of azobenzene. This model reproduces the collective photoisomerization kinetics of the azo stars in good agreement with theory and previous experiments. We then apply light of various intensities and wavelengths on an equilibrated columnar stack of azo stars in water. The simulations indicate that the aggregate does not break into separate fragments upon light irradiation. Instead, the stack develops defects in the form of molecular shifts and reorientations and, as a result, it eventually loses its columnar shape. The mechanism and driving forces behind this order–disorder structural transition are clarified based on the simulations. In the end, we provide a new interpretation of the experimentally observed morphological changes. View Full-Text
Keywords: azobenzene; photoisomerization; photostationary state; multiphotochromic systems; supramolecular assembly; molecular dynamics; computer simulations azobenzene; photoisomerization; photostationary state; multiphotochromic systems; supramolecular assembly; molecular dynamics; computer simulations
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MDPI and ACS Style

Koch, M.; Saphiannikova, M.; Guskova, O. Cyclic Photoisomerization of Azobenzene in Atomistic Simulations: Modeling the Effect of Light on Columnar Aggregates of Azo Stars. Molecules 2021, 26, 7674. https://doi.org/10.3390/molecules26247674

AMA Style

Koch M, Saphiannikova M, Guskova O. Cyclic Photoisomerization of Azobenzene in Atomistic Simulations: Modeling the Effect of Light on Columnar Aggregates of Azo Stars. Molecules. 2021; 26(24):7674. https://doi.org/10.3390/molecules26247674

Chicago/Turabian Style

Koch, Markus, Marina Saphiannikova, and Olga Guskova. 2021. "Cyclic Photoisomerization of Azobenzene in Atomistic Simulations: Modeling the Effect of Light on Columnar Aggregates of Azo Stars" Molecules 26, no. 24: 7674. https://doi.org/10.3390/molecules26247674

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