Hydrothermal crystallization pathways of amorphous ceric phosphate gels were found to be determined by the ammonia concentration in a reaction medium. This allows for highly selective hydrothermal synthesis of various finely crystal-

Two new cerium(IV) phosphates were obtained: cerium(IV) hydroxidophosphate, Ce(OH)PO4, and cerium(IV) oxidophosphate, Ce2O(PO4)2, which were shown to complement the classes of isostructural compounds M(OH)PO4 and R2O(PO4)2, where M=Th, U and R=Th, U, Np, Zr. Ce2O(PO4)2 oxidophosphate is formed by elimination of H2O from the crystal structure of Ce(OH)PO4 during its thermal decomposition. The structures of Ce(OH)PO4 and Ce2O(PO4)2 are related to each other with the same Cmce space group and similar unit cell parameters (a=6.9691(3) Å, b=9.0655(4) Å, c=12.2214(4) Å, V=772.13(8) Å3, Z=8; a=7.0220(4) Å, b=8.9894(5) Å, c=12.544(1) Å, V=791.8(1) Å3, Z=4, respectively).

Intermetallic compounds with semiconducting properties are rare, but they give rise to advanced materials for energy conversion and saving applications. Here, we present ReGa2Ge, a new electron-precise narrow-gap intermetallic semiconductor. The compound crystallizes in the IrIn3 structure type (space group P42/mnm, a = 6.5734(3) Å, c = 6.7450(8) Å, and Z = 4), where Re atoms occupy the Ir site, while Ga and Ge jointly populate the In sites. 69,71Ga nuclear quadrupole resonance spectroscopy indicates nonstatistical partially ordered distribution of Ga and Ge over two available crystallographic sites; however, the Ga:Ge ratio is exactly 2:1 without noticeable homogeneity range. The stoichiometry of ReGa2Ge ensures its precise valence electron count, which is 17 e– per formula unit. Accordingly, a narrow energy gap opens up at the Fermi energy in the electronic structure. Electrical resistivity, Seebeck coefficient, and thermal conductivity are in agreement with the semiconducting behavior deduced from the electronic structure calculations and point to prospective thermoelectric properties at high temperatures. Bonding analysis reveals dominant covalency in Re–E (E = Ga, Ge) and Re–Re interactions.