A Redox-Active Bridging Ligand to Promote Spin Delocalization, High-Spin Complexes, and Magnetic Multi-Switchability

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

doi:10.1002/anie.201803842

A Redox-Active Bridging Ligand to Promote Spin Delocalization, High-Spin Complexes, and Magnetic Multi-Switchability

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

50 Citations (SciVal)

Abstract

A dinuclear Co^II 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 T_1/2≈470 K for the pristine compound (n=4) to single-molecule magnet with an S_T=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.

Original language	English
Pages (from-to)	7841-7845
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	26
Early online date	30 Apr 2018
DOIs	https://doi.org/10.1002/anie.201803842
Publication status	Published - 25 Jun 2018

Funding

This work was supported by the ANR (ANR-16-CE29-0001-01, Active-Magnet project), the University of Bordeaux, the Région Nouvelle Aquitaine, the CNRS, the MOLSPIN COST action CA15128 and the CSC for the PhD funding of X.M. E.A.S. thanks EPSRC for support (EP/N006895/1), the IRIDIS High Performance Computing Facility and associated services at the University of Southampton and the RSC for a travel grant. The authors thank also D. Woodruff, J.-L. Liu, A. Mondal, and S. Exiga for their assistance and fruitful discussions as well as the GdR MCM-2: Magnétisme et Commutation Moléculaires.

Keywords

molecular magnetism
multiswitchability
non-innocent ligands
radicals
spin delocalization

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.201803842

Cite this

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title = "A Redox-Active Bridging Ligand to Promote Spin Delocalization, High-Spin Complexes, and Magnetic Multi-Switchability",

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.",

keywords = "molecular magnetism, multiswitchability, non-innocent ligands, radicals, spin delocalization",

author = "Xiaozhou Ma and Suturina, {Elizaveta A.} and Siddhartha De and Philippe N{\'e}grier and Mathieu Rouzi{\`e}res and Rodolphe Cl{\'e}rac and Pierre Dechambenoit",

year = "2018",

month = jun,

day = "25",

doi = "10.1002/anie.201803842",

language = "English",

volume = "57",

pages = "7841--7845",

journal = "Angewandte Chemie - International Edition",

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publisher = "John Wiley and Sons Inc.",

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T1 - A Redox-Active Bridging Ligand to Promote Spin Delocalization, High-Spin Complexes, and Magnetic Multi-Switchability

AU - Ma, Xiaozhou

AU - Suturina, Elizaveta A.

AU - De, Siddhartha

AU - Négrier, Philippe

AU - Rouzières, Mathieu

AU - Clérac, Rodolphe

AU - Dechambenoit, Pierre

PY - 2018/6/25

Y1 - 2018/6/25

N2 - 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.

AB - 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.

KW - molecular magnetism

KW - multiswitchability

KW - non-innocent ligands

KW - radicals

KW - spin delocalization

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U2 - 10.1002/anie.201803842

DO - 10.1002/anie.201803842

M3 - Article

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SN - 1433-7851

VL - 57

SP - 7841

EP - 7845

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 26

ER -

A Redox-Active Bridging Ligand to Promote Spin Delocalization, High-Spin Complexes, and Magnetic Multi-Switchability

Abstract

Funding

Keywords

ASJC Scopus subject areas

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Elizaveta Suturina

High Performance Computing (HPC) Facility

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A Redox-Active Bridging Ligand to Promote Spin Delocalization, High-Spin Complexes, and Magnetic Multi-Switchability

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Profiles

Elizaveta Suturina

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High Performance Computing (HPC) Facility

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