Centrosymmetric [N(CH3)4]2TiF6 vs. noncentrosymmetric polar [C(NH2)3]2TiF6: A hydrogen-bonding effect on the out-of-center distortion of TiF6 octahedra

The syntheses, structures, and characterization of organically templated zero-dimensional titanium fluoride materials, A2TiF6 (A[N(CH3)4] or [C(NH2)3]), are reported. Phase pure samples of A2TiF6 were synthesized by either solvothermal reaction method or a simple mixing method. While [N(CH3)4]2TiF6 crystallizes in a centrosymmetric space group, R-3, [C(NH2)3]2TiF6 crystallizes in a noncentrosymmetric polar space group, Cm. The asymmetric out-of-center distortion of TiF6 octahedra in polar [C(NH2)3]2TiF6 are attributable to the hydrogen-bonding interactions between the fluorine atoms in TiF6 octahedra and the nitrogen atoms in the [C(NH2)3]+ cation. Powder second-harmonic generation (SHG) measurements on the [C(NH2)3]2TiF6, using 1064 nm radiation, indicate the material has SHG efficiency of 25× that of α-SiO2, which indicates an average nonlinear optical susceptibility, 〈deff〉exp of 2.8 pm/V. Additional SHG measurements reveal that the material is not phase-matchable (Type 1). The magnitudes of out-of-center distortions and dipole moment calculations for TiF6 octahedra will be also reported.

Graphical abstractThe out-of-center distortion of TiF6 octahedron in the polar noncentrosymmetric [C(NH2)3]2TiF6 is attributable to the hydrogen-bonding interactions between the F in TiF6 octahedron and the H–N in the [C(NH2)3]+.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Two titanium fluorides materials have been synthesized in high yields. ► Hydrogen-bonds are crucial for the out-of-center distortion of TiF6 octahedra. ► [C(NH2)3]2TiF6 has a SHG efficiency of 25× that of α-SiO2.