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The study od magnetodielectric behaviors in frustrated Cu2Te2O5Br2 compoundChin, Yi-Pin 22 July 2011 (has links)
An intriguing magnetodielectric behavior is observed in triangular or tetrahedral frustrated and low-dimensional system. Therefore, the spin-tetrahedral and low-dimensional compound copper-tellurides (Cu2Te2O5Br2) is suggested that has magnetodielectric behavior. Tetragonal Cu2Te2O5Br2 contains clusters of four Cu2+ (S = 1/2) in a planar coordination. These tetrahedral form weakly coupled sheets within the crystallographic a-b plane. Therefore, this system is ideal to study the interplay between the spin frustration on a tetrahedron with localized low-energy excitations and collective magnetism induced by inter-tetrahedral couplings. In this material a strongly reduced magnetic transition temperature To = 11.5 K in comparison with a dominant magnetic exchange of 30 K is found. Low-dimensional systems with triangular geometries are considered as prominent candidates for applications using novel magnetoelectric materials. At the highest applied magnetic field 90 kOe, the temperature dependent dielectric behavior with almost frequency independent well defined maxima at Tm ~ 30 K and To ~ 11.5 K are enhanced compared with that at zero field. We suggest that the observed magnetodielectric coupling can arise from exchange striction involving frustrated tetramer clusters and inter-cluster exchange bridges with polarizable lone-pair electrons on Te4+ ions.
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Magnetic superexchange interactions: trinuclear bis(oxamidato) versus bis(oxamato) type complexesAbdulmalic, Mohammad A., Aliabadi, Azar, Petr, Andreas, Krupskaya, Yulia, Kataev, Vladislav, Büchner, Bernd, Zaripov, Ruslan, Vavilova, Evgeniya, Voronkova, Violeta, Salikov, Kev, Hahn, Torsten, Kortus, Jens, Meva, Francois Eya'ane, Schaarschmidt, Dieter, Rüffer, Tobias 09 June 2015 (has links) (PDF)
The diethyl ester of o-phenylenebis(oxamic acid) (opbaH2Et2) was treated with an excess of RNH2 in MeOH to cause the exclusive formation of the respective o-phenylenebis(N(R)-oxamides) (opboH4R2, R = Me 1, Et 2, nPr 3) in good yields. Treatment of 1–3 with half an equivalent of [Cu2(AcO)4(H2O)2] or one equivalent of [Ni(AcO)2(H2O)4] followed by the addition of four equivalents of [nBu4N]OH resulted in the formation of mononuclear bis(oxamidato) type complexes [nBu4N]2[M(opboR2)] (M = Ni, R = Me 4, Et 5, nPr 6; M = Cu, R = Me 7, Et 8, nPr 9). By addition of two equivalents of [Cu(pmdta)(NO3)2] to MeCN solutions of 7–9, novel trinuclear complexes [Cu3(opboR2)(L)2](NO3)2 (L = pmdta, R = Me 10, Et 11, nPr 12) could be obtained. Compounds 4–12 have been characterized by elemental analysis and NMR/IR spectroscopy. Furthermore, the solid state structures of 4–10 and 12 have been determined by single-crystal X-ray diffraction studies. By controlled cocrystallization, diamagnetically diluted 8 and 9 (1%) in the host lattice of 5 and 6 (99%) (8@5 and 9@6), respectively, in the form of single crystals have been made available, allowing single crystal ESR studies to extract all components of the g-factor and the tensors of onsite CuA and transferred NA hyperfine (HF) interaction. From these studies, the spin density distribution of the [Cu(opboEt2)]2− and [Cu(opbonPr2)]2− complex fragments of 8 and 9, respectively, could be determined. Additionally, as a single crystal ENDOR measurement of 8@5 revealed the individual HF tensors of the N donor atoms to be unequal, individual estimates of the spin densities on each N donor atom were made. The magnetic properties of 10–12 were studied by susceptibility measurements versus temperature to give J values varying from −96 cm−1 (10) over −104 cm−1 (11) to −132 cm−1 (12). These three trinuclear CuII-containing bis(oxamidato) type complexes exhibit J values which are comparable to and slightly larger in magnitude than those of related bis(oxamato) type complexes. In a summarizing discussion involving experimentally obtained ESR results (spin density distribution) of 8 and 9, the geometries of the terminal [Cu(pmdta)]2+ fragments of 12 determined by crystallographic studies, together with accompanying quantum chemical calculations, an approach is derived to explain these phenomena and to conclude if the spin density distribution of mononuclear bis(oxamato)/bis(oxamidato) type complexes could be a measure of the J couplings of corresponding trinuclear complexes. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
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Magnetic superexchange interactions: trinuclear bis(oxamidato) versus bis(oxamato) type complexesAbdulmalic, Mohammad A., Aliabadi, Azar, Petr, Andreas, Krupskaya, Yulia, Kataev, Vladislav, Büchner, Bernd, Zaripov, Ruslan, Vavilova, Evgeniya, Voronkova, Violeta, Salikov, Kev, Hahn, Torsten, Kortus, Jens, Meva, Francois Eya'ane, Schaarschmidt, Dieter, Rüffer, Tobias 09 June 2015 (has links)
The diethyl ester of o-phenylenebis(oxamic acid) (opbaH2Et2) was treated with an excess of RNH2 in MeOH to cause the exclusive formation of the respective o-phenylenebis(N(R)-oxamides) (opboH4R2, R = Me 1, Et 2, nPr 3) in good yields. Treatment of 1–3 with half an equivalent of [Cu2(AcO)4(H2O)2] or one equivalent of [Ni(AcO)2(H2O)4] followed by the addition of four equivalents of [nBu4N]OH resulted in the formation of mononuclear bis(oxamidato) type complexes [nBu4N]2[M(opboR2)] (M = Ni, R = Me 4, Et 5, nPr 6; M = Cu, R = Me 7, Et 8, nPr 9). By addition of two equivalents of [Cu(pmdta)(NO3)2] to MeCN solutions of 7–9, novel trinuclear complexes [Cu3(opboR2)(L)2](NO3)2 (L = pmdta, R = Me 10, Et 11, nPr 12) could be obtained. Compounds 4–12 have been characterized by elemental analysis and NMR/IR spectroscopy. Furthermore, the solid state structures of 4–10 and 12 have been determined by single-crystal X-ray diffraction studies. By controlled cocrystallization, diamagnetically diluted 8 and 9 (1%) in the host lattice of 5 and 6 (99%) (8@5 and 9@6), respectively, in the form of single crystals have been made available, allowing single crystal ESR studies to extract all components of the g-factor and the tensors of onsite CuA and transferred NA hyperfine (HF) interaction. From these studies, the spin density distribution of the [Cu(opboEt2)]2− and [Cu(opbonPr2)]2− complex fragments of 8 and 9, respectively, could be determined. Additionally, as a single crystal ENDOR measurement of 8@5 revealed the individual HF tensors of the N donor atoms to be unequal, individual estimates of the spin densities on each N donor atom were made. The magnetic properties of 10–12 were studied by susceptibility measurements versus temperature to give J values varying from −96 cm−1 (10) over −104 cm−1 (11) to −132 cm−1 (12). These three trinuclear CuII-containing bis(oxamidato) type complexes exhibit J values which are comparable to and slightly larger in magnitude than those of related bis(oxamato) type complexes. In a summarizing discussion involving experimentally obtained ESR results (spin density distribution) of 8 and 9, the geometries of the terminal [Cu(pmdta)]2+ fragments of 12 determined by crystallographic studies, together with accompanying quantum chemical calculations, an approach is derived to explain these phenomena and to conclude if the spin density distribution of mononuclear bis(oxamato)/bis(oxamidato) type complexes could be a measure of the J couplings of corresponding trinuclear complexes. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
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