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

• DOI: 10.1039/c9cp06590c
• Publication Date: 2020-03-09T09:04:16Z
• Authors: Laura Le Bras; Roxanne Berthin; Ismaïl Hamdi; Maroua Louati; Stéphane Aloïse; Michinori Takeshita; Carlo Adamo; Aurélie Perrier
• Keywords: Supramolecular Polymers; Supramolecular assembly; Molecular self-assembly

A dithienylethene (DTE) photochromic compound functionalized by ureidopyrimidinone (UPy) quadruple hydrogen bonding blocks was synthesized 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 assemblies only observed for one DTE isomer, namely closed-form isomer. To rationalize this experimental finding, with help Molecular Dynamics (MD) (time-dependent) DFT calculations, behaviour open-form monomers, dimers, hexamers π-stacked dimers solution is investigated. Our simulations show that, oligomers, progression assembly hindered due (i) possible very stable cyclic dimer parallel (ii) relative flexibility oligomers compared their counterparts, (iii) existence that constitute bottlenecks blocking self-assembly.