N-Substituted Benzene-1-Urea-3,5-Biscarboxamide (BUBA): Easily Accessible C-2-Symmetric Monomers for the Construction of Reversible and Chirally Amplified Helical Assemblies

Autor(es)

Li, Yan ^[1] ; Dubreucq, Ludovic ^[1] ; Alvarenga, Bruno G. ^{[2, 1]} ; Raynal, Matthieu ^[1] ; Bouteiller, Laurent ^[1]

Afiliação do(s) autor(es)

^[1] Sorbonne Univ, CNRS, Inst Parisien Chim Mol, Equipe Chim Polymeres, 4 Pl Jussieu, F-75005 Paris - France

^[2] Univ Estadual Campinas, UNICAMP, Dept Phys Chem, Inst Chem, Campinas, SP - Brazil

• Tipo de documento: Artigo Científico
• Fonte: CHEMISTRY-A EUROPEAN JOURNAL; v. 25, n. 45 JULY 2019.
• Citações Web of Science: 0

Resumo

Non-C-3-symmetric supramolecular helices are gaining interest for the design of hierarchical assemblies, for the compartmentalisation or the self-assembly of polymer chains and for application in asymmetric catalysis. Herein, N-substituted benzene-1-urea-3,5-biscarboxamide (BUBA) monomers, which consist of one urea and two carbon-connected amide functions linked to an aromatic ring, are introduced as an easily accessible class of C-2-symmetric supramolecular synthons. In apolar solvents, BUBA monomers assemble into long helical assemblies by means of hydrogen-bonding and aromatic interactions, as assessed by several analytical techniques. To probe the influence of the urea function, BUBA and related benzene-1,3,5-tricarboxamide (BTA) helical polymers have been compared, in terms of their thermodynamics of formation, stability, reversibility and chiral amplification properties. Similar to BTA, BUBA monomers form long helices reversibly through a highly cooperative mechanism and the helicity of their assemblies is governed by chiral amplification effects. However, precise quantification of their properties reveals that BUBA monomers assemble in a more cooperative manner. Also, chiral amplification operates to a higher extent in BUBA helices, as probed by both sergeants-and-soldiers and majority-rules experiments. Compatibility between urea and amide functions also allows the formation of co-assemblies that incorporate both BUBA and BTA monomers. Importantly, a small amount of chiral BUBA monomers in these co-assemblies is sufficient to obtain single-handed helices; thus paving the way towards the development of functional supramolecular helices. (AU)

• Processo FAPESP: 14/04515-8 - Polímeros supramoleculares de bis-ureias em solução: o balanço das interações soluto-solvente
• Beneficiário: Bruno Giordano Alvarenga
• Modalidade de apoio: Bolsas no Brasil - Doutorado