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A redox-active bridging ligand to promote spin delocalization, high-spin complexes, and magnetic multi-switchability

A redox-active bridging ligand to promote spin delocalization, high-spin complexes, and magnetic multi-switchability
A redox-active bridging ligand to promote spin delocalization, high-spin complexes, and magnetic multi-switchability

A dinuclear CoII complex, [Co2(tphz)(tpy)2]n+ (n=4, 3 or 2; tphz: tetrapyridophenazine; tpy: terpyridine), has been assembled using the redox-active and strongly complexing tphz bridging ligand. The magnetic properties of this complex can be tuned from spin-crossover with T1/2≈470 K for the pristine compound (n=4) to single-molecule magnet with an ST=5/2 spin ground state when once reduced (n=3) to finally a diamagnetic species when twice reduced (n=2). The two successive and reversible reductions are concomitant with an increase of the spin delocalization within the complex, promoting remarkably large magnetic exchange couplings and high-spin species even at room temperature.

molecular magnetism, multiswitchability, non-innocent ligands, radicals, spin delocalization
1433-7851
7841-7845
Ma, Xiaozhou
38d17b38-088b-40f8-8a27-04928694ec32
Suturina, Elizaveta A.
24dd007d-949a-4852-99d1-ea42b00103ef
De, Siddhartha
647d41fb-d5e7-4af0-b82f-377c92c6691e
Négrier, Philippe
b7e32da0-8f80-442d-8a6a-3ea6d006f339
Rouzières, Mathieu
8c6cfe8b-afbe-4ab9-8c3c-65bf94056b4e
Clérac, Rodolphe
3bd1d496-4135-49b8-a78b-600a88cbccf5
Dechambenoit, Pierre
1d92207f-fdb7-4329-8906-8b4c8062461f
Ma, Xiaozhou
38d17b38-088b-40f8-8a27-04928694ec32
Suturina, Elizaveta A.
24dd007d-949a-4852-99d1-ea42b00103ef
De, Siddhartha
647d41fb-d5e7-4af0-b82f-377c92c6691e
Négrier, Philippe
b7e32da0-8f80-442d-8a6a-3ea6d006f339
Rouzières, Mathieu
8c6cfe8b-afbe-4ab9-8c3c-65bf94056b4e
Clérac, Rodolphe
3bd1d496-4135-49b8-a78b-600a88cbccf5
Dechambenoit, Pierre
1d92207f-fdb7-4329-8906-8b4c8062461f

Ma, Xiaozhou, Suturina, Elizaveta A., De, Siddhartha, Négrier, Philippe, Rouzières, Mathieu, Clérac, Rodolphe and Dechambenoit, Pierre (2018) A redox-active bridging ligand to promote spin delocalization, high-spin complexes, and magnetic multi-switchability. Angewandte Chemie International Edition, 57 (26), 7841-7845. (doi:10.1002/anie.201803842).

Record type: Article

Abstract

A dinuclear CoII complex, [Co2(tphz)(tpy)2]n+ (n=4, 3 or 2; tphz: tetrapyridophenazine; tpy: terpyridine), has been assembled using the redox-active and strongly complexing tphz bridging ligand. The magnetic properties of this complex can be tuned from spin-crossover with T1/2≈470 K for the pristine compound (n=4) to single-molecule magnet with an ST=5/2 spin ground state when once reduced (n=3) to finally a diamagnetic species when twice reduced (n=2). The two successive and reversible reductions are concomitant with an increase of the spin delocalization within the complex, promoting remarkably large magnetic exchange couplings and high-spin species even at room temperature.

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More information

e-pub ahead of print date: 30 April 2018
Published date: 25 June 2018
Keywords: molecular magnetism, multiswitchability, non-innocent ligands, radicals, spin delocalization

Identifiers

Local EPrints ID: 424953
URI: https://eprints.soton.ac.uk/id/eprint/424953
ISSN: 1433-7851
PURE UUID: 8ddb8df9-583d-4db0-a21a-6701041938cd

Catalogue record

Date deposited: 05 Oct 2018 16:30
Last modified: 05 Oct 2018 16:30

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Contributors

Author: Xiaozhou Ma
Author: Elizaveta A. Suturina
Author: Siddhartha De
Author: Philippe Négrier
Author: Mathieu Rouzières
Author: Rodolphe Clérac
Author: Pierre Dechambenoit

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