| Ferromagnetic coupling and spin canting behaviour in heterobimetallic Re(IV)M(II/III) (M = Co(II/III), Ni(II)) species. | |
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MedLine Citation:
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PMID: 23154657 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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Three novel heterobimetallic Re(iv) compounds of formulae [ReBr(4)(μ-ox)M(4,7-Cl(2)phen)(2)]·CH(3)CN·CH(3)NO(2) [M = Co(ii) () and Ni(ii) ()] and [ReBr(4)(ox)](3)[Co(III)(5,6-dmphen)(3)](2)·CH(3)CN·2CH(3)NO(2)·4H(2)O () [ox = oxalate, 4,7-Cl(2)phen = 4,7-dichloro-1,10-phenanthroline and 5,6-dmphen = 5,6-dimethyl-1,10-phenanthroline] have been synthesised and the structures of and determined by single crystal X-ray diffraction. Compound is an oxalato-bridged Re(IV)Co(II) heterodinuclear complex where the [ReBr(4)(ox)](2-) unit acts as a bidentate ligand towards the [Co(4,7-Cl(2)phen)(2)](2+) entity, the separation between Re(iv) and Co(ii) across the oxalate being 5.482(1) Å. Compound is an ionic salt whose structure is made up of [Re(IV)Br(4)(ox)](2-) anions and [Co(III)(5,6-dmphen)(3)](3+) cations plus acetonitrile, nitromethane and water as solvent molecules. The magnetic properties of were investigated in the temperature range 1.9-300 K. Relatively large ferromagnetic interactions between Re(iv) and M(ii) through the bis(bidentate) oxalato occur in and [J(ReM) = +11.0 () and +12.2 cm(-1) (), the Hamiltonian being defined as Ĥ = -J(ReM)Ŝ(Re)·Ŝ(M)] which are explained on the basis of orbital symmetry considerations. A behaviour typical of a magnetically diluted Re(iv) complex with a large and positive value of zero-field splitting for the ground level (D(Re) = +43 cm(-1)) is observed for in the high temperature range, whereas it exhibits spin canting in the low temperature domain as well as magnetic ordering below ca. 4.8 K. |
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Authors:
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José Martínez-Lillo; Donatella Armentano; Giovanni De Munno; Miguel Julve; Francesc Lloret; Juan Faus |
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Publication Detail:
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Type: JOURNAL ARTICLE Date: 2012-11-15 |
Journal Detail:
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Title: Dalton transactions (Cambridge, England : 2003) Volume: - ISSN: 1477-9234 ISO Abbreviation: Dalton Trans Publication Date: 2012 Nov |
Date Detail:
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Created Date: 2012-11-16 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 101176026 Medline TA: Dalton Trans Country: - |
Other Details:
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Languages: ENG Pagination: - Citation Subset: - |
Affiliation:
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Departamento de Química Inorgánica/Instituto de Ciencia Molecular, Facultad de Química de la Universidad de Valencia, Dr. Moliner 50, 46100, Burjassot, Valencia, Spain. lillo@uv.es. |
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