Synthesis, structure, and characterization of new Li+-d0-lone-pair-oxides: noncentrosymmetric polar Li6(Mo2O5)3(SeO3)6 and centrosymmetric Li2(MO3)(TeO3) (M = Mo6+ or W6+).

New quaternary lithium-d(0) cation-lone-pair oxides, Li(6)(Mo(2)O(5))(3)(SeO(3))(6) (Pmn2(1)) and Li(2)(MO(3))(TeO(3)) (P2(1)/n) (M = Mo(6+) or W(6+)), have been synthesized and characterized. The former is noncentrosymmetric and polar, whereas the latter is centrosymmetric. Their crystal structures exhibit zigzag anionic layers composed of distorted MO(6) and asymmetric AO(3) (A = Se(4+) or Te(4+)) polyhedra. The anionic layers stack along a 2-fold screw axis and are separated by Li(+) cations. Powder SHG measurements on Li(6)(Mo(2)O(5))(3)(SeO(3))(6) using 1064 nm radiation reveal a SHG efficiency of approximately 170 × α-SiO(2). Particle size vs SHG efficiency measurements indicate Li(6)(Mo(2)O(5))(3)(SeO(3))(6) is type 1 nonphase-matchable. Converse piezoelectric measurements result in a d(33) value of ∼28 pm/V and pyroelectric measurements reveal a pyroelectric coefficient of -0.43 μC/m(2)K at 50 °C for Li(6)(Mo(2)O(5))(3)(SeO(3))(6). Frequency-dependent polarization measurements confirm that Li(6)(Mo(2)O(5))(3)(SeO(3))(6) is nonferroelectric, i.e., the macroscopic polarization is not reversible, or 'switchable'. Infrared, UV-vis, thermogravimetric, and differential thermal analysis measurements and electron localization function calculations were also done for all materials.