Polar hexagonal tungsten bronze-type oxides: KNbW2O9, RbNbW2O9, and KTaW2O9.

The synthesis, crystal structures, second-harmonic generation (SHG), piezoelectric, pyroelectric, and ferroelectric properties of three polar noncentrosymmetric (NCS) hexagonal tungsten bronze-type oxides are reported. The materials KNbW 2O 9, RbNbW 2O 9, and KTaW 2O 9 were synthesized by standard solid-state techniques and structurally characterized by laboratory powder X-ray diffraction. The compounds are isostructural, crystallizing in the polar NCS space group Cmm2. The materials exhibit a corner-shared MO 6 (M = Nb (5+)/W (6+) or Ta (5+)/W (6+)) octahedral framework, with K (+) or Rb (+) occupying the "hexagonal" tunnels. The d (0) transition metals, Nb (5+), Ta (5+), and W (6+), are displaced from the center of their oxide octahedra attributable to second-order Jahn-Teller effects. SHG measurements using 1064 nm radiation revealed frequency-doubling efficiencies ranging from 180 to 220 x alpha-SiO 2. Converse piezoelectric measurements resulted in d 33 values ranging from 10 to 41 pm V (-1). The total pyroelectric coefficient, p, at 50 degrees C ranged from -6.5 to -34.5 muC K (-1) m (-2). The reported materials are also ferroelectric, as demonstrated by hysteresis loops (polarization vs electric field). Spontaneous polarization values, P s, ranging from 2.1 to 8.4 muC cm (-2) were measured. The magnitudes of the SHG efficiency, piezoelectric response, pyroelectric coefficient, and ferroelectric polarization are strongly dependent on the out-of-center distortion of the d (0) transition metals. Structure-property relationships are discussed and explored. Crystal data: KNbW 2O 9, orthorhombic, space group Cmm2 (No. 35), a = 21.9554(2) A, b = 12.60725(15) A, c = 3.87748(3) A, V = 1073.273(13) A (3), and Z = 6; RbNbW 2O 9, orthorhombic, space group Cmm2 (No. 35), a = 22.00985(12) A, b = 12.66916(7) A, c = 3.8989(2) A, V = 1086.182(10) A (3), and Z = 6; KTaW 2O 9, orthorhombic, space group Cmm2 (No. 35), a = 22.0025(2) A, b = 12.68532(14) A, c = 3.84456(4) A, V = 1073.05(2) A (3), and Z = 6.