Complex structures arising from the self-assembly of a simple organic salt
Type
ArticleAuthors
Montis, Riccardo
Fusaro, Luca

Falqui, Andrea

Hursthouse, Michael B.
Tumanov, Nikolay

Coles, Simon J.

Threlfall, Terry L.
Horton, Peter N.
Sougrat, Rachid
Lafontaine, Anaïs
Coquerel, Gérard
Rae, A. David
KAUST Department
Biological and Environmental Science and Engineering (BESE) DivisionBioscience Program
Electron Microscopy
Date
2021-02-10Online Publication Date
2021-02-10Print Publication Date
2021-02-11Embargo End Date
2021-08-10Submitted Date
2019-03-19Permanent link to this record
http://hdl.handle.net/10754/667405
Metadata
Show full item recordAbstract
Molecular self-assembly is the spontaneous association of simple molecules into larger and ordered structures<sup>1</sup>. It is the basis of several natural processes, such as the formation of colloids, crystals, proteins, viruses and double-helical DNA<sup>2</sup>. Molecular self-assembly has inspired strategies for the rational design of materials with specific chemical and physical properties<sup>3</sup>, and is one of the most important concepts in supramolecular chemistry. Although molecular self-assembly has been extensively investigated, understanding the rules governing this phenomenon remains challenging. Here we report on a simple hydrochloride salt of fampridine that crystallizes as four different structures, two of which adopt unusual self-assemblies consisting of polyhedral clusters of chloride and pyridinium ions. These two structures represent Frank-Kasper (FK) phases of a small and rigid organic molecule. Although discovered in metal alloys<sup>4,5</sup> more than 60 years ago, FK phases have recently been observed in several classes of supramolecular soft matter<sup>6-11</sup> and in gold nanocrystal superlattices<sup>12</sup> and remain the object of recent discoveries<sup>13</sup>. In these systems, atoms or spherical assemblies of molecules are packed to form polyhedra with coordination numbers 12, 14, 15 or 16. The two FK structures reported here crystallize from a dense liquid phase and show a complexity that is generally not observed in small rigid organic molecules. Investigation of the precursor dense liquid phase by cryogenic electron microscopy reveals the presence of spherical aggregates with sizes ranging between 1.5 and 4.6 nanometres. These structures, together with the experimental procedure used for their preparation, invite interesting speculation about their formation and open different perspectives for the design of organic crystalline materials.Citation
Montis, R., Fusaro, L., Falqui, A., Hursthouse, M. B., Tumanov, N., Coles, S. J., … Rae, A. D. (2021). Complex structures arising from the self-assembly of a simple organic salt. Nature, 590(7845), 275–278. doi:10.1038/s41586-021-03194-ySponsors
We thank the UK Engineering and Physical Sciences Research Council for financial support for single-crystal diffraction facilities through funding of the UK National Crystallography Service. R.M. thanks R. Davey (The University of Manchester) for comments and discussions. We thank M. Sanselme (Université de Rouen Normandie) for help with in situ X-ray diffraction measurements. We thank the technological platform “Physico-Chemical Characterization” – PC2 (University of Namur) for providing resources used for this research.Publisher
Springer NatureJournal
NaturePubMed ID
33568820Additional Links
http://www.nature.com/articles/s41586-021-03194-yRelations
Is Supplemented By:- [Dataset]
Coles, S., Montis, R., Horton, P., & Hursthouse, M. (2019). Single crystal diffraction raw data for Fampridine hydrochloride Phase 4 [Data set]. Zenodo. https://doi.org/10.5281/ZENODO.2593677. DOI: 10.5281/zenodo.2593677 Handle: 10754/667705 - [Dataset]
Coles, S., Montis, R., Horton, P., & Hursthouse, M. (2019). Single crystal diffraction raw data for Fampridine hydrochloride Phase 3 [Data set]. Zenodo. https://doi.org/10.5281/ZENODO.2593670. DOI: 10.5281/zenodo.2593670 Handle: 10754/667706 - [Dataset]
Coles, S. I., Montis, R., Horton, P., & Hursthouse, M. (2019). Single crystal diffraction raw data for Fampridine hydrochloride Phase 2 [Data set]. Zenodo. https://doi.org/10.5281/ZENODO.2585776. DOI: 10.5281/zenodo.2585776 Handle: 10754/667708 - [Dataset]
Coles, S., Montis, R., Horton, P., & Hursthouse, M. (2019). Single crystal diffraction raw data for Fampridine hydrochloride Phase 1 [Data set]. Zenodo. https://doi.org/10.5281/ZENODO.2595089. DOI: 10.5281/zenodo.2595089 Handle: 10754/667761 - [Dataset]
Montis, Riccardo, Fusaro, Luca, Falqui, Andrea, Hursthouse, Michael B., Tumanov, Nikolay, Coles, Simon J., Threlfall, Terry L., Horton, Peter N., Sougrat, Rachid, Lafontaine, Anaïs, Coquerel, Gérard, & Rae, A. David. (2021). CCDC 1540141: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/CCDC.CSD.CC1NPMZY. DOI: 10.5517/ccdc.csd.cc1npmzy Handle: 10754/669192 - [Dataset]
Montis, Riccardo, Fusaro, Luca, Falqui, Andrea, Hursthouse, Michael B., Tumanov, Nikolay, Coles, Simon J., Threlfall, Terry L., Horton, Peter N., Sougrat, Rachid, Lafontaine, Anaïs, Coquerel, Gérard, & Rae, A. David. (2021). CCDC 1540139: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/CCDC.CSD.CC1NPMXW. DOI: 10.5517/ccdc.csd.cc1npmxw Handle: 10754/669193 - [Dataset]
Montis, Riccardo, Fusaro, Luca, Falqui, Andrea, Hursthouse, Michael B., Tumanov, Nikolay, Coles, Simon J., Threlfall, Terry L., Horton, Peter N., Sougrat, Rachid, Lafontaine, Anaïs, Coquerel, Gérard, & Rae, A. David. (2021). CCDC 1540140: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/CCDC.CSD.CC1NPMYX. DOI: 10.5517/ccdc.csd.cc1npmyx Handle: 10754/669194 - [Dataset]
Montis, Riccardo, Fusaro, Luca, Falqui, Andrea, Hursthouse, Michael B., Tumanov, Nikolay, Coles, Simon J., Threlfall, Terry L., Horton, Peter N., Sougrat, Rachid, Lafontaine, Anaïs, Coquerel, Gérard, & Rae, A. David. (2021). CCDC 1897427: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/CCDC.CSD.CC21PFBJ. DOI: 10.5517/ccdc.csd.cc21pfbj Handle: 10754/669196 - [Dataset]
Montis, Riccardo, Fusaro, Luca, Falqui, Andrea, Hursthouse, Michael B., Tumanov, Nikolay, Coles, Simon J., Threlfall, Terry L., Horton, Peter N., Sougrat, Rachid, Lafontaine, Anaïs, Coquerel, Gérard, & Rae, A. David. (2021). CCDC 1897428: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/CCDC.CSD.CC21PFCK. DOI: 10.5517/ccdc.csd.cc21pfck Handle: 10754/669197
ae974a485f413a2113503eed53cd6c53
10.1038/s41586-021-03194-y
Scopus Count
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