{Mo102}型纳米多孔无机富勒烯衍生物的合成、表征及三阶非线性光学性质

在室温酸性条件下, 利用高负电性的表面分布有20个{Mo9O9}型纳米孔道的无机富勒烯囊状阴离子{(MoⅥ)Mo5ⅥO21(H2O)6}12{Mo2ⅤO4(SO4)}30]72-与胍基乙酸反应, 得到了表面分布有20个{Mo6O6}型纳米孔道的由102个Mo及氧原子组成的{(Mo)Mo5O21(H2O)4SO4}12{MoⅤO(H2O)}30]12-小无机富勒烯囊状阴离子. 通过单晶X射线衍射、元素分析、FTIR、UV-Vis、TG-DTA、ESR等手段对其进行了表征. 该化合物属于三斜晶系, P1空间群, 晶胞参数a=2.5377(5) nm, b=2.5932(5) nm, c=3.9547(8) nm, α =83.58(3) °, β=86.15(3) °, γ=75.55(3) °, V=25.023(9) nm3. 利用脉冲时间为5 ns的532 nm激光通过Z-扫描实验得到该化合物的三阶非线性折射率γ=-3.29×10-18 m2/W, 三阶非线性极化率χ(3)=-1.04×10-23 m2·V-2, 表明该化合物具有较强的自散焦三阶非线性光学效应.

Synthesis, Characterization and the Third-order Nonlinear Optical Properties of a Derivative of {Mo102}-type Porous Inorganic Nano-fullerene

A small spherical inorganic fullerene nano-capsule anion of a formula {(Mo)Mo5O21(H2O)4·SO4}12{MoⅤO(H2O)}30]12- bearing 20 {Mo6O6}-type rings/channels built up from 102 Mo atoms and O atoms were synthesized by reacting a highly charged spherical inorganic fullerene nano-capsule anion with the formula {(MoⅥ)Mo5ⅥO21(H2O)6}12{Mo2ⅤO4(SO4)}30]72- bearing 20 {Mo9O9}-type rings/channels with guanidineacetic acid under acidic conditions at room temperature. The crystal structure of the resulted compound were characterized by X-ray single-crystal diffraction, elemental analysis, TG-DTA analysis and FTIR, UV-Vis, and ESR spectrascopies. It crystallizes in a triclinic system space group P1, a=2.5377(5) nm, b=2.5932(5) nm, c=3.9547(8) nm, α=83.58(3) °, β=86.15(3) °, γ=75.55(3) °, V=25.023(9) nm3. Meanwhile, its third-order nonlinear optical properties were studied using Z-scan technique with 5 ns laser pulse at λ=532 nm. The third-order nonlinear refractive index of the title compound is determined to be γ=-3.29×10-18 m2/W and the third-order nonlinear susceptibility χ(3)=-1.04×10-23 m2·V-2, showing strong nonlinear self-defocusing refractive effects.