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Electron Spin Density on the N-Donor Atoms of Cu(II)–(Bis)oxamidato Complexes As Probed by a Pulse ELDOR Detected NMR B

Aliabadi, Azar, Zaripov, Ruslan, Salikhov, Kev, Voronkova, Violeta, Vavilova, Evgeniya, Abdulmalic, Mohammad A., Rüffer, Tobias, Büchner, Bernd, Kataev, Vladislav
The Journal of physical chemistry 2015 v.119 no.43 pp. 13762-13770
asymmetry, copper, crystals, models, nickel, nitrogen, nuclear magnetic resonance spectroscopy, physical chemistry, stable isotopes
We have applied the pulse ELDOR detected NMR (EDNMR) technique to determine the tensors of the transferred Cu (S = 1/2) – ¹⁴N (I = 1) hyperfine (HF) interaction in single crystals of diamagnetically diluted mononuclear o-phenylenebis(N(R)-oxamide) complexes of [ⁿBu₄N]₂[Cu(opboR₂)] (R = Et 1, ⁿPr 2) (1%) in a host lattice of [ⁿBu₄N]₂[Ni(opboR₂)] (R = Et 3, ⁿPr 4) (99%) (1@3 and 2@4)). To facilitate the analysis of our EDNMR data and to analyze possible manifestations of the nuclear quadrupole interaction in the EDNMR spectra, we have treated a model electron–nuclear system of the coupled S = 1/2 and I = 1 spins using the spin density matrix formalism. It appears that this interaction yields a peculiar asymmetry of the EDMR spectra that manifests not only in the shift of the positions of the EDNMR lines that correspond to the forbidden EPR transitions, as expected, but also in the intensities of the EDNMR lines. The symmetric shape of the experimental spectra suggests the conclusion that, in the studied complexes, the quadrupole interaction is negligible. This has simplified the analysis of the spectra. The HF tensors of all four N donor atoms could be accurately determined. On the basis of the HF tensors, an estimate of the spin density transferred from the central paramagnetic Cu(II) ion to the N donor atoms reveals its unequal distribution. We discuss possible implications of our estimates for the magnetic exchange paths and interaction strengths in respective trinuclear complexes [Cu₃(opboR₂) (pmdta)₂](NO₃)₂ (R = Et 6, ⁿPr 7).