The A7B7O30 structural type is
a columnar-perovskite-type arrangement originally evidenced in La7Mo7O30 [Goutenoire et al. J.
Solid State Chem. 1999, 142, 228], an intermediate reduction product of fast oxide-ion conductor
La2Mo2O9. Subsequently, this new
structural family has been extended to La7W6+
4M5+
3O30 (M = Nb, Ta)
[Goutenoire et al. J. Solid State Chem.
2005, 178, 2811]. Here we show that it is possible to
further extend the solid solution through partial substitution of
hexavalent tungsten by di-, tri-, or tetravalent transition metals.
The general formula is La3+
7W6+
7‑x
M
m+
x
O30 with x =
3/(6 – m), or m = 6 –
3/x. Single phase samples with M
m+ = Zn2+, Fe3+, and Ti4+ have
been prepared, and their crystal structure refined using X-ray powder
diffraction. In the structure, the transition metal with lower valence
is preferentially located in the octahedral site shared by consecutive
trans-connected perovskite cages, whose diagonal runs along the threefold
axis of the structure. Close similarities are noticed with the cationic
repartition and distortion of coordination polyhedra in compounds
belonging to the A
n
B
n
O3n+2 series of layered perovskites.
A rationale is proposed, which includes the A7B7O30 structural type as a subsequent 1D step to the 3D
→ 2D A
n
B
n
O3n+2 scheme of perovskite framework
slicing by progressive oxygen insertion through decreasing n.