Synthesis, cation ordering and magnetic properties of the
(Sb1-xPbx)2(Mn1-ySby)O4
solid solutions with the
Sb2MnO4-type structure
Chemistry of Materials, 17, 1123 (2005)
A.M. Abakumov,a
M.G. Rozova,a
E.V. Antipov,a
J. Hadermann,b
G. Van Tendeloo,b
M.V. Lobanov,c
M. Greenblatt,c
M. Croft,d
E.V. Tsiper,e,f
A. Llobet,g
K.A. Lokshing
and Y. Zhaog
aDepartment of Chemistry, Moscow State University, Moscow 119992, Russia bEMAT, University of Antwerp, Gronenborgerlaan 171, B-2020 Antwerp, Belgium cDepartment of Chemistry, Rutgers University, Piscataway, NJ 08854, USA dDepartment of Physics and Astronomy, Rutgers University, Piscataway, NJ 08854, USA eSchool of Computational Sciences, George Mason University, Fairfax, VA 22303 fCenter for Computational Materials Science, Naval Research Laboratory, Washington, DC 20375 gLANSCE-12, Los Alamos National Laboratory, Los Alamos, NM 87544, USA
Single phase
(Sb1-xPbx)2(Mn1-ySby)O4
(0.02MnO4-type structure were prepared at 650 C by
solid state reaction in evacuated sealed silica tubes. A replacement
of Sb by Pb results in the oxidation of Sb+3 to Sb,+5 which in turn replaces Mn+2 cations in octahedrally coordinated
positions within the infinite rutile-type chains. The crystal
structures of
Pb0.44Sb1.64Mn0.92O4,
Pb0.75Sb1.48Mn0.77O4,
Pb1.07Sb1.26Mn0.67O4
and
Pb1.186Sb1.175Mn0.639O4
were refined from X-ray powder diffraction data. Increasing the Pb
content leads to a decrease of the a parameter from a=8.719(2)A to
a=8.6131(8)A and to an increase of the c parameter from c=5.999(2)A to
c=6.2485(7)A (for
Sb2MnO4 and
Pb1.216Sb1.155Mn0.628O4,
respectively). This occurs due to increasing average cation size at
the Pb/Sb position and decreasing cation size at the Mn/Sb position
that leads to strong deformation of the
(Mn/Sb)O6 octahedra. Starting from the
Pb0.75Sb1.48Mn0.77O4
composition a modulated structure with q=gc* was observed by electron diffraction.
High resolution electron microscopy observations revealed that Mn and
Sb ions order forming layers of octahedrally coordinated positions
filled either by Mn+2 or by Sb+5 cations and alternating along the c
axis. the dilution of the magnetic Mn+2 cations by non-magnetic Sb+5 entities leads to a suppression of the
antiferromagnetic intrachain interaction and disappearance of
long-range magnetic order at high doping level. At T=20K the Axy spin component was found to be dominant
at the AFM structure of the
Pb0.44Sb1.64Mn0.92O4
sample by neutron diffraction.
Computational studies of low dimensional functional materials
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