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Complex structures arising from the self-assembly of a simple organic salt

Complex structures arising from the self-assembly of a simple organic salt
Complex structures arising from the self-assembly of a simple organic salt
Molecular self-assembly is the spontaneous association of simple molecules into larger and ordered structures.1 It is the basis of several natural processes, such as the formation of colloids, crystals, the generation of proteins, viruses and double helical DNA.2 Molecular self-assembly has inspired strategies for the rational design of materials with specific chemical/physical properties,3 becoming perhaps one of the most fascinating and important concepts in supramolecular chemistry. Here we report on a simple hydrochloride salt of fampridine which crystallises as four different structures, two of which adopt unusual self-assemblies consisting of polyhedral clusters of chloride and pyridinium ions. These two structures represent the first observation of Frank Kasper (FK) phases of a small and rigid organic molecule. Although discovered in metal alloys 4-5 more than 60 years ago, FK phases have recently been observed in several classes of supramolecular soft matter 6-11 and in gold nanocrystal superlattices12 and still are the object of new discoveries.13 In these systems, atoms or spherical assemblies of molecules are packed to form polyhedra with coordination numbers (CN) 12, 14, 15 or 16. The two FK structures reported here crystallise from a dense liquid phase and show a complexity that is generally not observed in the case of rigid and small organic molecules. Investigation of the precursor dense liquid phase by cryo-EM reveals the presence of spherical aggregates with size ranging between 1.5 and 5 nm. These structures, together with the experimental procedure used for their preparation, invite interesting considerations on the route to their formation and open new perspectives for the design of a new generation of organic crystalline materials.
0028-0836
275-278
Montis, Riccardo
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Fusaro, Luca
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Falqui, Andrea
e6168df9-5fe7-4089-888f-35519f737d93
Hursthouse, Michael
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Tumanov, Nikolay
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Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Threlfall, Terry L.
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Horton, Peter
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Sougrat, Rachid
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Lafontaine, Anaïs
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Coquerel, Gerard
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Rae, A. David
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Montis, Riccardo
2d2d60eb-b455-414a-80d8-d5a58002bd92
Fusaro, Luca
c5263aa2-8b1b-4aaf-9469-68570e26d4a0
Falqui, Andrea
e6168df9-5fe7-4089-888f-35519f737d93
Hursthouse, Michael
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Tumanov, Nikolay
5e4fc1c6-c2a7-4330-8e08-c319d5a6f910
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Threlfall, Terry L.
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Horton, Peter
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Sougrat, Rachid
a36ca304-d26b-4073-8ed3-2ae5ce7e9fa6
Lafontaine, Anaïs
fac2df47-538d-44a5-af73-9488a15a667a
Coquerel, Gerard
5fa14766-56b5-489c-8ce1-2f81e5a75c43
Rae, A. David
7686ce76-1e7a-47a7-b145-a8efaffa85b6

Montis, Riccardo, Fusaro, Luca, Falqui, Andrea, Hursthouse, Michael, Tumanov, Nikolay, Coles, Simon J., Threlfall, Terry L., Horton, Peter, Sougrat, Rachid, Lafontaine, Anaïs, Coquerel, Gerard and Rae, A. David (2021) Complex structures arising from the self-assembly of a simple organic salt. Nature, 590 (7845), 275-278. (doi:10.1038/s41586-021-03194-y).

Record type: Article

Abstract

Molecular self-assembly is the spontaneous association of simple molecules into larger and ordered structures.1 It is the basis of several natural processes, such as the formation of colloids, crystals, the generation of proteins, viruses and double helical DNA.2 Molecular self-assembly has inspired strategies for the rational design of materials with specific chemical/physical properties,3 becoming perhaps one of the most fascinating and important concepts in supramolecular chemistry. Here we report on a simple hydrochloride salt of fampridine which crystallises as four different structures, two of which adopt unusual self-assemblies consisting of polyhedral clusters of chloride and pyridinium ions. These two structures represent the first observation of Frank Kasper (FK) phases of a small and rigid organic molecule. Although discovered in metal alloys 4-5 more than 60 years ago, FK phases have recently been observed in several classes of supramolecular soft matter 6-11 and in gold nanocrystal superlattices12 and still are the object of new discoveries.13 In these systems, atoms or spherical assemblies of molecules are packed to form polyhedra with coordination numbers (CN) 12, 14, 15 or 16. The two FK structures reported here crystallise from a dense liquid phase and show a complexity that is generally not observed in the case of rigid and small organic molecules. Investigation of the precursor dense liquid phase by cryo-EM reveals the presence of spherical aggregates with size ranging between 1.5 and 5 nm. These structures, together with the experimental procedure used for their preparation, invite interesting considerations on the route to their formation and open new perspectives for the design of a new generation of organic crystalline materials.

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Accepted/In Press date: 12 November 2020
e-pub ahead of print date: 10 February 2021

Identifiers

Local EPrints ID: 447480
URI: http://eprints.soton.ac.uk/id/eprint/447480
ISSN: 0028-0836
PURE UUID: 5d6e5e6f-15db-4fa2-952b-ce7b5c92bec1
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for Peter Horton: ORCID iD orcid.org/0000-0001-8886-2016

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Date deposited: 12 Mar 2021 17:31
Last modified: 21 Aug 2021 04:01

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Contributors

Author: Riccardo Montis
Author: Luca Fusaro
Author: Andrea Falqui
Author: Nikolay Tumanov
Author: Simon J. Coles ORCID iD
Author: Terry L. Threlfall
Author: Peter Horton ORCID iD
Author: Rachid Sougrat
Author: Anaïs Lafontaine
Author: Gerard Coquerel
Author: A. David Rae

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