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

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 helices25451065010661FAPESP – Fundação de Amparo à Pesquisa Do Estado De São Paulo2014/04515-8This work was supported by the China Scholarship Council (CSC; PhD grant to Y.L.) Jacques Jestin (LLB, Saclay) is acknowledged for assistance with SANS experiments. B.G.A. thanks the Sao Paulo Research Foundation (FAPESP, Sao Paulo, Brazil) for a fellowship (2014/04515‐8