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Understanding the properties of dithienylethenes functionalized for supramolecular self-assembly: a molecular modeling study.

Title: Understanding the properties of dithienylethenes functionalized for supramolecular self-assembly: a molecular modeling study.
Authors: Le Bras, Laurine; Berthin, R.; Hamdi, Ismaïl; Louati, M.; Aloise, Stephane; Takeshita, M.; Adamo, Carlo; Perrier, Aurélie
Contributors: Université de Lille; CNRS; Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL ENSCP; Institute of Chemistry for Life and Health Sciences iCLeHS; Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 LASIRE; Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516; Institut Universitaire de France IUF
Publication Year: 2024
Collection: LillOA (Lille Open Archive - Université de Lille)
Description: A dithienylethene (DTE) photochromic compound functionalized by ureidopyrimidinone (UPy) quadruple hydrogen bonding blocks was synthesized by Takeshita and coworkers [Takeshita et al., Chem. Commun., 2005, 761] in order to form a light-responsive supramolecular self-assembling system. In solution, the formation of supramolecular assemblies was only observed for one DTE isomer, namely the closed-form isomer. To rationalize this experimental finding, with the help of Molecular Dynamics (MD) and (time-dependent) DFT calculations, the behaviour of open-form and closed-form monomers, dimers, hexamers and π-stacked dimers in solution is investigated. Our simulations show that, for the open-form oligomers, the progression of the supramolecular assembly is hindered due to (i) the possible formation of a very stable cyclic dimer for the open-form parallel isomer, (ii) the relative flexibility of the open-form oligomers compared to their closed-form counterparts, and (iii) the possible existence of π-stacked dimers that constitute bottlenecks blocking the progression of the supramolecular self-assembly.
Document Type: article in journal/newspaper
Language: English
Relation: Physical Chemistry Chemical Physics; Phys Chem Chem Phys; http://hdl.handle.net/20.500.12210/109564
Availability: https://hdl.handle.net/20.500.12210/109564
Rights: info:eu-repo/semantics/closedAccess
Accession Number: edsbas.8EA0C499
Database: BASE