1D magnetic interactions in Cu Oxovanadium Phosphates (VPO), magnetic susceptibility, DFT, and single-crystal EPR

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dc.creatorVenegas Yazigi, Diego
dc.creatorSpodine, Evgenia
dc.creatorSaldias, Marianela
dc.creatorVega, Andrés
dc.creatorParedes García, Verónica
dc.creatorCalvo, Rafael
dc.creatorSantana, Ricardo Costa de
dc.date.accessioned2024-07-11T13:26:06Z
dc.date.available2024-07-11T13:26:06Z
dc.date.issued2015
dc.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 P1̅ 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 (dCu–Cu = 5.07 Å; J defined as Hex(i,j) = −J Si·Sj), considering dinuclear units for 1, and J = −1.44 cm–1 (dCu–Cu = 3.47 Å) 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 |J′| > 0.3 cm–1 for 1 (dCu–Cu = 5.54 Å) and a smaller value of |J′| ≥ 0.15 cm–1 for 2 (dCu–Cu = 6.59 Å). DFT calculations allow evaluating two different exchange couplings for each compound, specifically, J = −36.60 cm–1 (dCu–Cu = 5.07 Å) and J′ = 0.20 cm–1 (dCu–Cu =5.54 Å) for 1 and J = −1.10 cm–1 (dCu–Cu =3.47 Å) and J′ = 0.01 cm–1 (dCu–Cu = 6.59 Å) 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.
dc.identifier.citationVENEGAS-YAZIGI, Diego; SPODINE, Evgenia; SALDIAS, Marianela; VEGA, Andrés; PAREDES-GARCÍA, Verónica; CALVO, Rafael; SANTANA, Ricardo Costa de. 1D magnetic interactions in Cu Oxovanadium Phosphates (VPO), magnetic susceptibility, DFT, and single-crystal EPR. Inorganic Chemistry, Washington, v. 54, p. 3805-3814, 2015. DOI: 10.1021/ic503045d. Disponível em: https://pubs.acs.org/doi/10.1021/ic503045d. Acesso em: 23 maio 2023.
dc.identifier.doi10.1021/ic503045d
dc.identifier.issn0020-1669
dc.identifier.issne- 1520-510X
dc.identifier.urihttps://pubs.acs.org/doi/10.1021/ic503045d
dc.language.isoeng
dc.publisher.countryEstados unidos
dc.publisher.departmentInstituto de Física - IF (RMG)
dc.rightsAcesso Restrito
dc.title1D magnetic interactions in Cu Oxovanadium Phosphates (VPO), magnetic susceptibility, DFT, and single-crystal EPR
dc.typeArtigo

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