Structural chemistry and magnetic properties of Ln18Li8Rh(5-x)Fe(x)O39 (Ln = La, Nd).
Polycrystalline samples of Ln(18)Li(8)Rh(5-x)Fe(x)O(39) (Ln = La, Nd; 0.5 < or = x < or = 5) have been synthesized by a solid-state method and studied by a combination of dc and ac magnetometry, neutron diffraction, and Mossbauer spectroscopy. All compositions adopt a cubic structure (space group Pm3n, a(0) approximately 12 A) based on intersecting 111 chains made up of alternating octahedral and trigonal-prismatic coordination sites. These chains occupy channels within a Ln-O framework. At low values of x, iron preferentially occupies the smaller (2a) of the two distinct octahedral sites as low-spin Fe(IV). The Rh(III) on the larger (8e) octahedral site is replaced by high-spin Fe(III). Nd-containing compositions having x > 1 show spin-glass-like behavior below approximately 5 K. La-containing compositions having x > 1 show evidence of a magnetic transition at approximately 8 K, but the nature of the transition is unclear. This contrasting behavior demonstrates that, although the structural chemistry of the two systems is essentially the same, the magnetic character of the Ln cations plays an important role in determining the properties of these compounds.
Inorganic Chemistry Laboratory, Oxford University, South Parks Road, Oxford OX1 3QR, United Kingdom. peter.battle@chem.ox.ac.uk
Peter D
PD
Battle
Siân E
SE
Dutton
Nirawat
N
Thammajak
Fernande
F
Grandjean
Moulay T
MT
Sougrati
Gary J
GJ
Long
Katsuyoshi
K
Oh-ishi
Shinji
S
Nakanishi