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Using Redox-Active π Bridging Ligand as a Control Switch of Intramolecular Magnetic Interactions Full article

Journal Journal of the American Chemical Society
ISSN: 0002-7863 , E-ISSN: 1520-5126
Output data Year: 2019, Volume: 141, Number: 19, Pages: 7721-7725 Pages count : 5 DOI: 10.1021/jacs.9b03044
Tags GROUND-STATE; COMPLEXES
Authors Ma Xiaozhou 1,2 , Suturina Elizaveta A. 3 , Rouzières Mathieu 1,2 , Platunov Mikhail 4 , Wilhelm Fabrice 4 , Rogalev Andrei 4 , Clérac Rodolphe 1,2 , Dechambenoit Pierre 1,2
Affiliations
1 CNRS, CRPP, UMR 5031, Pessac F-33600, France
2 Univ. Bordeaux, CRPP, UMR 5031, Pessac F-33600, France
3 Centre for Sustainable Chemical Technologies (CSCT), University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom
4 ESRF-The European Synchrotron, CS 40220, 38043 Grenoble Cedex 9, France

Abstract: Intramolecular magnetic interactions in the dinuclear complexes [(tpy)Ni(tphz)Ni(tpy)](n+) (n = 4, 3, and 2; tpy, terpyridine; tphz, tetrapyridophenazine) were tailored by changing the oxidation state of the pyrazine-based bridging ligand. While its neutral form mediates a weak antiferromagnetic (AF) coupling between the two S = 1 Ni(II), its reduced form, tphz(center dot-), promotes a remarkably large ferromagnetic exchange of +214(5) K with Ni(II) spins. Reducing twice the bridging ligand affords weak Ni-Ni interactions, in marked contrast to the Co(II) analogue. Those experimental results, supported by a careful examination of the involved orbitals, provide a clear understanding of the factors which govern strength and sign of the magnetic exchange through an aromatic bridging ligand, a prerequisite for the rational design of strongly coupled molecular systems and high T-C molecule-based magnets.
Cite: Ma X. , Suturina E.A. , Rouzières M. , Platunov M. , Wilhelm F. , Rogalev A. , Clérac R. , Dechambenoit P.
Using Redox-Active π Bridging Ligand as a Control Switch of Intramolecular Magnetic Interactions
Journal of the American Chemical Society. 2019. V.141. N19. P.7721-7725. DOI: 10.1021/jacs.9b03044 WOS Scopus РИНЦ AN OpenAlex
Files: Full text from publisher
Dates:
Submitted: Mar 27, 2019
Published online: Apr 26, 2019
Published print: May 15, 2019
Identifiers:
Web of science: WOS:000468366900013
Scopus: 2-s2.0-85065758947
Elibrary: 38980541
Chemical Abstracts: 2019:847238
OpenAlex: W2941160447
Citing:
DB Citing
Web of science 29
Scopus 29
OpenAlex 28
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