Mechanical interlocking of molecules (catenation) is a nontrivial challenge in modern synthetic chemistry and materials science1,2. One strategy to achieve catenation is the design of pre-annular molecules that are capable of both efficient cyclization and of pre-organizing another precursor to engage in subsequent interlocking3–9. This task is particularly difficult when the annular target is composed of a large ensemble of molecules, that is, when it is a supramolecular assembly. However, the construction of such unprecedented assemblies would enable the visualization of nontrivial nanotopologies through microscopy techniques, which would not only satisfy academic curiosity but also pave the way to the development of materials with nanotopology-derived properties. Here we report the synthesis of such a nanotopology using fibrous supramolecular assemblies with intrinsic curvature. Using a solvent-mixing strategy, we kinetically organized a molecule that can elongate into toroids with a radius of about 13 nanometres. Atomic force microscopy on the resulting nanoscale toroids revealed a high percentage of catenation, which is sufficient to yield ‘nanolympiadane’10, a nanoscale catenane composed of five interlocked toroids. Spectroscopic and theoretical studies suggested that this unusually high degree of catenation stems from the secondary nucleation of the precursor molecules around the toroids. By modifying the self-assembly protocol to promote ring closure and secondary nucleation, a maximum catenation number of 22 was confirmed by atomic force microscopy.
Self-assembled poly-catenanes from supramolecular toroidal building blocks / Datta, S.; Kato, Y.; Higashiharaguchi, S.; Aratsu, K.; Isobe, A.; Saito, T.; Prabhu, D. D.; Kitamoto, Y.; Hollamby, M. J.; Smith, A. J.; Dagleish, R.; Mahmoudi, N.; Pesce, L.; Perego, C.; Pavan, G. M.; Yagai, S.. - In: NATURE. - ISSN 0028-0836. - 583:7816(2020), pp. 400-405. [10.1038/s41586-020-2445-z]
Self-assembled poly-catenanes from supramolecular toroidal building blocks
Pavan G. M.;
2020
Abstract
Mechanical interlocking of molecules (catenation) is a nontrivial challenge in modern synthetic chemistry and materials science1,2. One strategy to achieve catenation is the design of pre-annular molecules that are capable of both efficient cyclization and of pre-organizing another precursor to engage in subsequent interlocking3–9. This task is particularly difficult when the annular target is composed of a large ensemble of molecules, that is, when it is a supramolecular assembly. However, the construction of such unprecedented assemblies would enable the visualization of nontrivial nanotopologies through microscopy techniques, which would not only satisfy academic curiosity but also pave the way to the development of materials with nanotopology-derived properties. Here we report the synthesis of such a nanotopology using fibrous supramolecular assemblies with intrinsic curvature. Using a solvent-mixing strategy, we kinetically organized a molecule that can elongate into toroids with a radius of about 13 nanometres. Atomic force microscopy on the resulting nanoscale toroids revealed a high percentage of catenation, which is sufficient to yield ‘nanolympiadane’10, a nanoscale catenane composed of five interlocked toroids. Spectroscopic and theoretical studies suggested that this unusually high degree of catenation stems from the secondary nucleation of the precursor molecules around the toroids. By modifying the self-assembly protocol to promote ring closure and secondary nucleation, a maximum catenation number of 22 was confirmed by atomic force microscopy.File | Dimensione | Formato | |
---|---|---|---|
Preprint-nofigs.pdf
accesso aperto
Tipologia:
1. Preprint / submitted version [pre- review]
Licenza:
PUBBLICO - Tutti i diritti riservati
Dimensione
235.71 kB
Formato
Adobe PDF
|
235.71 kB | Adobe PDF | Visualizza/Apri |
Self-assembled_poly-catenanes_from_supramolecular.pdf
non disponibili
Tipologia:
2a Post-print versione editoriale / Version of Record
Licenza:
Non Pubblico - Accesso privato/ristretto
Dimensione
6.71 MB
Formato
Adobe PDF
|
6.71 MB | Adobe PDF | Visualizza/Apri Richiedi una copia |
Postprint-Accepted-version.pdf
Open Access dal 16/01/2021
Tipologia:
2. Post-print / Author's Accepted Manuscript
Licenza:
PUBBLICO - Tutti i diritti riservati
Dimensione
4.34 MB
Formato
Adobe PDF
|
4.34 MB | Adobe PDF | Visualizza/Apri |
Pubblicazioni consigliate
I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
https://hdl.handle.net/11583/2844692