Stimuli-controlled self-assembly of diverse tubular aggregates from one single small monomer.

Shi, Qixun; Javorskis, Tomas; Bergquist, Karl-Erik; Ulčinas, Artūras; Niaura, Gediminas; Matulaitienė, Ieva; Orentas, Edvinas; Wärnmark, Kenneth · Nat Commun · 2017

basic_science · Level V

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Abstract

The design and synthesis of new stimuli-responsive hydrogen-bonding monomers that display a diversity of self-assembly pathways is of central importance in supramolecular chemistry. Here we describe the aggregation properties of a simple, intrinsically C<sub>2</sub>-symmetric enantiopure bicyclic cavity compound bearing a terminally unsubstituted ureidopyrimidinone fragment fused with a pyrrole moiety in different solvents and in the absence and presence of C<sub>60</sub> and C<sub>70</sub> guests. The tetrameric cyclic aggregate is selectively obtained in chlorinated solvents, where only part of the available hydrogen bonding sites are utilized, whereas in toluene or upon addition of C<sub>70</sub> guests, further aggregation into tubular supramolecular polymers is achieved. The open-end cyclic assemblies rearrange into a closed-shell capsule upon introduction of C<sub>60</sub> with an accompanied symmetry breaking of the monomer. Our study demonstrates that a C<sub>60</sub> switch can be used to simultaneously control the topology and occupancy of tubular assemblies resulting from the aggregation of small monomers.