Novel alkaline earth copper germanates with ferro and antiferromagnetic S=1/2 chains
authors Brandao, P; Reis, MS; Gai, Z; dos Santos, AM
nationality International
journal JOURNAL OF SOLID STATE CHEMISTRY
author keywords Hydrothermal synthesis; Crystal structure; Copper germanates; Magnetic chains
keywords FRAMEWORK; BEHAVIOR
abstract Two new alkaline earth copper(II) germanates were hydrothermally synthesized: CaCuGeO4 center dot H2O (1) and BaCu2Ge3O9 center dot H2O (2), and their structures determined by single crystal X-ray diffraction. Compound (1) crystallizes in space group P2(1)/c with a=5.1320(2) angstrom, b=16.1637(5) angstrom, c=5.4818(2) angstrom, beta=102.609(2)degrees, V=443.76(3) angstrom(3) and Z=4. This copper germanate contains layers of composition [CuGeO4](infinity)(2-) comprising CuO4 square planes and GeO4 tetrahedra with calcium and water molecules in the inter-layer space. Compound (2) crystallizes in the Cmcm space group with a=5.5593(3) angstrom, b=10.8606(9) angstrom, c=13.5409(8) angstrom, V=817.56(9) angstrom(3) and Z=4. This structure contains GeO6 and CuO6 octahedra as well as GeO4 tetrahedra, forming a three-dimensional network of interconnecting six-membered ring channels. The magnetic susceptibility for both samples can be interpreted as S=1/2 chains, in agreement with the copper topology observed in the crystal structure. The susceptibility of (1) exhibits a Bonner-Fisher type behavior, resulting from antiferromagnetic intra-chain interactions without three-dimensional ordering down to 5 K-the lowest measured temperature. This observation, together with the absence of super-exchange paths between the copper chains, make this system particularly promising for the study of low dimensional magnetism. The magnetic properties of (2) show a very weak ferromagnetic near-neighbor interaction along the chain. In this compound a peak the chi T plot seems to indicate the onset of interchain antiferromagentic correlations. However, no ordering temperature is detected in the susceptibility data. Published by Elsevier Inc.
publisher ACADEMIC PRESS INC ELSEVIER SCIENCE
issn 0022-4596
year published 2013
volume 198
beginning page 39
ending page 44
digital object identifier (doi) 10.1016/j.jssc.2012.09.006
web of science category Chemistry, Inorganic & Nuclear; Chemistry, Physical
subject category Chemistry
unique article identifier WOS:000314320800006
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