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Exploiting host–guest chemistry to manipulate magnetic interactions in metallosupramolecular M4L6 tetrahedral cages

Exploiting host–guest chemistry to manipulate magnetic interactions in metallosupramolecular M4L6 tetrahedral cages
Exploiting host–guest chemistry to manipulate magnetic interactions in metallosupramolecular M4L6 tetrahedral cages
Reaction of Ni(OTf)2 with the bisbidentate quaterpyridine ligand L results in the self-assembly of a tetrahedral, paramagnetic cage [NiII4L6]8+. By selectively exchanging the bound triflate from [OTf⊂NiII4L6](OTf)7 (1), we have been able to prepare a series of host–guest complexes that feature an encapsulated paramagnetic tetrahalometallate ion inside this paramagnetic host giving [MIIX4⊂NiII4L6](OTf)6, where MIIX42− = MnCl42− (2), CoCl42− (5), CoBr42− (6), NiCl42− (7), and CuBr42− (8) or [MIIIX4⊂NiII4L6](OTf)7, where MIIIX4 = FeCl4 (3) and FeBr4 (4). Triflate-to-tetrahalometallate exchange occurs in solution and can also be accomplished through single-crystal-to-single-crystal transformations. Host–guest complexes 1–8 all crystallise as homochiral racemates in monoclinic space groups, wherein the four {NiN6} vertexes within a single Ni4L6 unit possess the same Δ or Λ stereochemistry. Magnetic susceptibility and magnetisation data show that the magnetic exchange between metal ions in the host [NiII4] complex, and between the host and the MX4n− guest, are of comparable magnitude and antiferromagnetic in nature. Theoretically derived values for the magnetic exchange are in close agreement with experiment, revealing that large spin densities on the electronegative X-atoms of particular MX4n− guest molecules lead to stronger host–guest magnetic exchange interactions.
1478-6524
5134-5142
Scott, Aaron J.
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Vallejo, Julia
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Sarkar, Arup
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Smythe, Lucy
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Martí, E. Regincós
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Nichol, Gary S.
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Klooster, Wim
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Coles, Simon J.
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Murrie, Mark
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Rajaraman, Gopalan
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Piligkos, Stergios
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Lusby, Paul J.
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Brechin, Euan K.
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Scott, Aaron J.
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Vallejo, Julia
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Sarkar, Arup
2c75b56f-d13b-4183-b7c9-09d7f22133e3
Smythe, Lucy
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Martí, E. Regincós
bbcac1ff-098c-4f58-9576-3369828e318c
Nichol, Gary S.
016249ad-f036-477d-9f6e-dd1bc619e372
Klooster, Wim
64dc0111-f415-4226-9189-45764c0933d9
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Murrie, Mark
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Rajaraman, Gopalan
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Piligkos, Stergios
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Lusby, Paul J.
7edd6163-af61-4425-83ef-bf48d9c9b094
Brechin, Euan K.
3f928747-2144-43c3-8ac8-9b2013437edc

Scott, Aaron J., Vallejo, Julia, Sarkar, Arup, Smythe, Lucy, Martí, E. Regincós, Nichol, Gary S., Klooster, Wim, Coles, Simon J., Murrie, Mark, Rajaraman, Gopalan, Piligkos, Stergios, Lusby, Paul J. and Brechin, Euan K. (2021) Exploiting host–guest chemistry to manipulate magnetic interactions in metallosupramolecular M4L6 tetrahedral cages. Chemical Science, 2021 (12), 5134-5142. (doi:10.1039/D1SC00647A).

Record type: Article

Abstract

Reaction of Ni(OTf)2 with the bisbidentate quaterpyridine ligand L results in the self-assembly of a tetrahedral, paramagnetic cage [NiII4L6]8+. By selectively exchanging the bound triflate from [OTf⊂NiII4L6](OTf)7 (1), we have been able to prepare a series of host–guest complexes that feature an encapsulated paramagnetic tetrahalometallate ion inside this paramagnetic host giving [MIIX4⊂NiII4L6](OTf)6, where MIIX42− = MnCl42− (2), CoCl42− (5), CoBr42− (6), NiCl42− (7), and CuBr42− (8) or [MIIIX4⊂NiII4L6](OTf)7, where MIIIX4 = FeCl4 (3) and FeBr4 (4). Triflate-to-tetrahalometallate exchange occurs in solution and can also be accomplished through single-crystal-to-single-crystal transformations. Host–guest complexes 1–8 all crystallise as homochiral racemates in monoclinic space groups, wherein the four {NiN6} vertexes within a single Ni4L6 unit possess the same Δ or Λ stereochemistry. Magnetic susceptibility and magnetisation data show that the magnetic exchange between metal ions in the host [NiII4] complex, and between the host and the MX4n− guest, are of comparable magnitude and antiferromagnetic in nature. Theoretically derived values for the magnetic exchange are in close agreement with experiment, revealing that large spin densities on the electronegative X-atoms of particular MX4n− guest molecules lead to stronger host–guest magnetic exchange interactions.

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Accepted/In Press date: 28 February 2021
e-pub ahead of print date: 1 March 2021

Identifiers

Local EPrints ID: 448340
URI: http://eprints.soton.ac.uk/id/eprint/448340
ISSN: 1478-6524
PURE UUID: d81b4e85-378f-422f-8f20-13ae2fa9eaae
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 20 Apr 2021 16:34
Last modified: 28 Apr 2021 01:36

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Contributors

Author: Aaron J. Scott
Author: Julia Vallejo
Author: Arup Sarkar
Author: Lucy Smythe
Author: E. Regincós Martí
Author: Gary S. Nichol
Author: Wim Klooster
Author: Simon J. Coles ORCID iD
Author: Mark Murrie
Author: Gopalan Rajaraman
Author: Stergios Piligkos
Author: Paul J. Lusby
Author: Euan K. Brechin

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