Crystalline, mixed-valence manganese analogue of prussian blue: magnetic, spectroscopic, X-ray and neutron diffraction studies.
The compound of stoichiometry Mn(II)3[Mn(III)(CN)6]2.zH2O (z = 12-16) (1) forms air-stable, transparent red crystals. Low-temperature single crystal optical spectroscopy and single crystal X-ray diffraction provide compelling evidence for N-bonded high-spin manganese(II), and C-bonded low-spin manganese(III) ions arranged in a disordered, face-centered cubic lattice analogous to that of Prussian Blue. X-ray and neutron diffraction show structured diffuse scattering indicative of partially correlated (rather than random) substitutions of [Mn(III)(CN)6] ions by (H2O)6 clusters. Magnetic susceptibility measurements and elastic neutron scattering experiments indicate a ferrimagnetic structure below the critical temperature Tc = 35.5 K.
Franz
Patrick
P
Departement für Chemie und Biochemie, Laboratorium für Kristallographie, Universität Bern, Freiestrasse 3, CH-3012 Bern, Switzerland.
Ambrus
Christina
C
Hauser
Andreas
A
Chernyshov
Dmitry
D
Hostettler
Marc
M
Hauser
Jürg
J
Keller
Lukas
L
Krämer
Karl
K
Stoeckli-Evans
Helen
H
Pattison
Philip
P
Bürgi
Hans-Beat
HB
Decurtins
Silvio
S