Supramolecular nesting of cyclic polymers

Kondratuk, Dmitry V.; Perdig�o, Luis M.A.; Esmail, Ayad M.S.; O'Shea, James N.; Beton, Peter H.; Anderson, Harry L.

Abstract

Advances in template-directed synthesis make it possible to create artificial molecules with protein-like dimensions, directly from simple components. These synthetic macromolecules have a proclivity for self-organization that is reminiscent of biopolymers. Here, we report the synthesis of monodisperse cyclic porphyrin polymers, with diameters of up to 21 nm (750 C–C bonds). The ratio of the intrinsic viscosities for cyclic and linear topologies is 0.72, indicating that these polymers behave as almost ideal flexible chains in solution. When deposited on ​gold surfaces, the cyclic polymers display a new mode of two-dimensional supramolecular organization, combining encapsulation and nesting; one nanoring adopts a near-circular conformation, thus allowing a second nanoring to be captured within its perimeter, in a tightly folded conformation. Scanning tunnelling microscopy reveals that nesting occurs in combination with stacking when nanorings are deposited under vacuum, whereas when they are deposited directly from solution under ambient conditions there is stacking or nesting, but not a combination of both.

Citation

Kondratuk, D. V., Perdigão, L. M., Esmail, A. M., O'Shea, J. N., Beton, P. H., & Anderson, H. L. (2015). Supramolecular nesting of cyclic polymers. Nature Chemistry, 7(4), 317-322. https://doi.org/10.1038/nchem.2182

• Journal Article Type: Article
• Acceptance Date: Jan 13, 2015
• Online Publication Date: Feb 16, 2015
• Publication Date: 2015-04
• Deposit Date: Jul 15, 2016
• Publicly Available Date: Jul 15, 2016
• Journal: Nature Chemistry
• Print ISSN: 1755-4330
• Electronic ISSN: 1755-4349
• Publisher: Nature Publishing Group
• Peer Reviewed: Peer Reviewed
• Volume: 7
• Issue: 4
• Pages: 317-322
• DOI: https://doi.org/10.1038/nchem.2182
• Keywords: Molecular self-assembly, Scanning probe microscopy, Self-assembly, Surface assembly
• Public URL: https://nottingham-repository.worktribe.com/output/744953
• Publisher URL: http://www.nature.com/nchem/journal/v7/n4/full/nchem.2182.html
• Additional Information: Received: 1 August 2014; Accepted: 13 January 2015; First Online: 16 February 2015; : The authors declare no competing financial interests.
• Contract Date: Jul 15, 2016