ABSTRACT
A series of disordered Ca1.5La0.5FeRuO6, CaLaFeRuO6 and La2FeRuO6 double perovskites were prepared by the solid-state reaction method and investigated by neutron powder diffraction, X-ray absorption near-edge structure (XANES) analysis at the Ru-K edge, Mössbauer spectroscopy, DC magnetization and resistivity measurements. All compounds crystallize in the orthorhombic crystal structure with the space group Pbnm down to 3 K, showing a random distribution of Fe and Ru at the B site. Thermogravimetric analysis indicates oxygen deficiency in the Ca-rich and formal oxygen hyperstoichiometry in the La-rich members of the present series. While Mössbauer spectra verify the Fe3+ state for all compositions, the XANES study reveals a variable Run+ oxidation state which decreases with increasing La content. The end member actually is a Ru3+/Ru4+ compound with possibly some cation vacancies. From magnetic susceptibility and neutron diffraction measurements, the presence of a G-type antiferromagnetic ordering was observed with a drastic increase in transition temperature from 275 K (Ca1.5La0.5FeRuO6) to 570 K (La2FeRuO6). Mössbauer spectroscopy confirms the presence of long-range ordering but, due to local variations in the exchange interactions, the magnetic states are microscopically inhomogeneous. All the samples are variable range hopping semiconductors. A complex interplay between structural features, charge states, anion or cation defects, and atomic disorder determines the magnetic properties of the present disordered 3d/4d double perovskite series.
ABSTRACT
Here we report a new three-dimensional nickel-based hybrid structure [Ni3(BTB)2(BPE)4(H2O)2]·2DMF·2H2O, 1 [where BTB = 1,3,5-tris(4-carboxyphenyl)benzene and BPE = 1,2-bis((4-pyridyl)ethane)], which exhibits long-range ferromagnetism and semiconductor behavior. The dipolar interaction between the magnetic spins is suggested to explain the development of long-range ferromagnetic ordering, where the superexchange interaction can be unwanted due to the large distance between the magnetic spins. Optical band gap and resistance vs. temperature measurements reveal the semiconductor nature of this compound. The density of states calculations shed light towards the origin of the low band gap value.
ABSTRACT
A magnetostructural correlation has been carried out for two newly synthesized two-fold-interpenetrated three-dimensional structures. Compound 1, denoted as [Ni(L1)(L2)]·2DMF (where L1 is 1,4-benzene-dicarboxylic acid (BDC), L2 is 4,4-oxybis-(N-(pyridine-4-yl)benzamide), and DMF is N,N'-dimethylformamide), was observed to have a three-dimensional structure with two-fold interpenetration. Compound 2, denoted as [Co(L3)(L2)]·2DMF (where L3 is 2,5-thiopehene-dicarboxylic acid (TDC)), was also observed to display a three-dimensional structure with an architecture identical to that of compound 1. Both compounds were well characterised using several techniques including single-crystal X-ray diffraction, powder X-ray diffraction, TGA, and IR. Magnetism and specific heat measurements of compound 1 revealed a canted-antiferromagnetic transition at TN ≈ 4 K and a field-induced spin-flop transition at a relatively low field strength. These exotic features were attributed to the low-symmetry space group P(1[combining macron]) and single-ion anisotropy of the Ni2+ sub-lattice. In contrast, compound 2 was found to be weakly antiferromagnetic in nature with a negligible interaction between the magnetic Co2+ ions.
