Document Detail

Ferromagnetic coupling and spin canting behaviour in heterobimetallic Re(IV)M(II/III) (M = Co(II/III), Ni(II)) species.
MedLine Citation:
PMID:  23154657     Owner:  NLM     Status:  Publisher    
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.
José Martínez-Lillo; Donatella Armentano; Giovanni De Munno; Miguel Julve; Francesc Lloret; Juan Faus
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-11-15
Journal Detail:
Title:  Dalton transactions (Cambridge, England : 2003)     Volume:  -     ISSN:  1477-9234     ISO Abbreviation:  Dalton Trans     Publication Date:  2012 Nov 
Date Detail:
Created Date:  2012-11-16     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101176026     Medline TA:  Dalton Trans     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Departamento de Química Inorgánica/Instituto de Ciencia Molecular, Facultad de Química de la Universidad de Valencia, Dr. Moliner 50, 46100, Burjassot, Valencia, Spain.
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