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1D Magnetic Interactions in CuII Oxovanadium Phosphates (VPO), Magnetic Susceptibility, DFT, and Single-Crystal EPR

Authordc.contributor.authorVenegas Yazigi, Diego 
Authordc.contributor.authorSpodine Spiridonova, Evgenia 
Authordc.contributor.authorSaldias, Marianela 
Authordc.contributor.authorVega, Andrés 
Authordc.contributor.authorParedes García, Verónica 
Authordc.contributor.authorCalvo, Rafael 
Authordc.contributor.authorSantana, Ricardo Costa de 
Cita de ítemdc.identifier.citationInorganic Chemistry, Volumen 54, Issue 8, 2015, Pages 3805-3814
Abstractdc.description.abstractWe report the crystal face indexing and molecular spatial orientation, magnetic properties, electron paramagnetic resonance (EPR) spectra, and density functional theory (DFT) calculations of two previously reported oxovanadium phosphates functionalized with CuII complexes, namely, [Cu(bipy)(VO2)(PO4)](n) (1) and [{Cu(phen)}(2)(VO2(H2O)(2))(H2PO4)(2) (PO4)](n) (2), where bipy = 2,2'-bipyridine and phen = 1,10-phenanthroline, obtained by a new synthetic route allowing the growth of single crystals appropriate for the EPR measurements. Compounds 1 and 2 crystallize in the triclinic group P1(-) and in the orthorhombic Pccn group, respectively, containing dinuclear copper units connected by two -O-P-O- bridges in 1 and by a single -O-P-O- bridge in 2, further connected through -O-P-O-V-O- bridges. We emphasize in our work the structural aspects related to the chemical paths that determine the magnetic properties. Magnetic susceptibility data indicate bulk antiferromagnetism for both compounds, allowing to calculate J = -43.0 cm(-1) (d(Cu-Cu) = 5.07 angstrom; J defined as H-ex(i,j) = -J S-i center dot S-j), considering dinuclear units for 1, and J = (-1).44 cm(-1) (d(Cu-Cu) = 3.47 angstrom) using the molecular field approximation for 2. The single-crystal EPR study allows evaluation of the g matrices, which provide a better understanding of the electronic structure. The absence of structure of the EPR spectra arising from the dinuclear character of the compounds allows estimation of weak additional exchange couplings vertical bar J'vertical bar > 0.3 cm(-1) for 1 (d(Cu-Cu) = 5.54 angstrom) and a smaller value of vertical bar J'vertical bar >= 0.15 cm(-1) for 2 (d(Cu-Cu) = 6.59 angstrom). DFT calculations allow evaluating two different exchange couplings for each compound, specifically, J = -36.60 cm(-1) (d(Cu-Cu) = 5.07 angstrom) and J' = 0.20 cm(-1) (d(Cu-Cu) =5.54 angstrom) for 1 and J = (-1).10 cm(-1) (d(Cu-Cu) =3.47 angstrom) and J' = 0.01 cm(-1) (d(Cu-Cu) = 6.59 angstrom) for 2, this last value being in the range of the uncertainties of the calculations. Thus, these values are in good agreement with those provided by magnetic and single-crystal EPR measurements.
Publisherdc.publisherAmerican Chemical Society
Type of licensedc.rightsAttribution-NonCommercial-NoDerivs 3.0 Chile
Link to Licensedc.rights.uri
Sourcedc.sourceInorganic Chemistry
Keywordsdc.subjectPhysical and Theoretical Chemistry
Keywordsdc.subjectInorganic chemistry
Títulodc.title1D Magnetic Interactions in CuII Oxovanadium Phosphates (VPO), Magnetic Susceptibility, DFT, and Single-Crystal EPR
Document typedc.typeArtículo de revista
Indexationuchile.indexArtículo de publicación SCOPUS

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