中文摘要：

Keggin 类型 phenylimido-polyoxometalates α-[ 下午 ₁₂ O ₃₉ NPh ]³⁻(M = W 和瞬间) 系统地在电子结构上被调查了，氧化还原作用象一样非线性光(NLO ) 由密度的性质功能的理论(DFT ) 。天赋证实的强壮的 M≡N 契约结合轨道(NBO ) 分析包括一张 s 契约和二张 π 契约，与 Mo≡N 在一样[瞬间 ₆ O ₁₈ NPh ]²⁻ 。而且， phenylimido 片断有效地修改 α- 的电子性质[下午 ₁₂ O ₃₉ NPh ]³⁻ 。一方面，当扩大时，inorganic 聚类从{瞬间 ₆ O ₁₈}到{ PMo ₁₂ O ₃₉},在在α-的人和 LUMO 之间的精力差距[ PMo ₁₂ O ₃₉ NPh ]³⁻减少了，为还原电位导致极其阳极的移动，当刺激精力是更少和全部的秒顺序 polarizability β 时，₀直到 438-3 ×1 0 ⁻³⁰ esu ，它比的大将近 10 倍[瞬间 ₆ O ₁₈ NPh ]²⁻。在另一方面，什么时候在 α- 的金属 W [下午 ₁₂ O ₃₉ NPh ]³⁻ 被瞬间代替，在瞬间和 N 之间的相互作用被提高，氧化还原作用能力变得更强壮。为 α- 的 β ₀ 价值[PMo ₁₂ O ₃₉ NPh ]³⁻ 比 α- 的高超过 5 倍[PW ₁₂ O ₃₉ NPh ]³⁻ 。它显示改变适当金属或扩大无机的簇将改进氧化还原作用性质和秒顺序非线性的反应。而且，为上面提及的三混合物的电子转变主要从 organoimido 片断发生了(作为电子施体) 到 polyanion 簇(作为领受人) 。作为结果， α-[PMo ₁₂ O ₃₉ NPh ]³⁻ 可以是氧化剂和非线性的光材料的一个有希望的候选人。增补材料为在 10.1007/s11434-008-0500-5 的这篇文章是可得到

英文摘要：

Keggin-type phenylimido-polyoxometalates α-[PM12O39NPh]^3- （M = W and Mo） have been systematically investigated on the electronic structures, redox as well as nonlinear optical （NLO） properties by density functional theory （DFT）. The strong M--N bond confirmed by natural bond orbital （NBO） analysis comprises one δ bond and two Tr bonds, the same as Mo=N in [Mo6O18NPh]^2-, Furthermore, phenylimido segment effectively modifies the electronic properties of α-[PM12O39NPh]^3-, On one hand, when enlarging the inorganic cluster from {MO6O18} to {PM012O39}, the energy gap between HOMO and LUMO in α-[PM12O39NPh]^3- decreased, resulting in enormously anodic shift for the reduction potential, while the excitation energy is less and the total second-order polarizability β0 is up to 438.3×10^-3 esu, which is nearly 10 times larger than that of [Mo6O18NPh]^2-. On the other hand, when metal W in α-[PM12O39NPh]^3- is substituted by Mo, the interaction between Mo and N is enhanced and the redox ability becomes stronger. The β0 value for α-[PM12O39NPh]^3- is more than 5 times higher than that of α-[PM12O39NPh]^3-. It indicates that changing appropriate metal or enlarging the inorganic cluster will improve the redox properties and second-order nonlinear response. Moreover, the electron transition for three compounds mentioned above occurred mainly from organoimido segment （as the electron donor） to polyanion cluster （as the acceptor）. As a result, α-[PM12O39NPh]^3- may be a promising candidate for oxidant and nonlinear optical material.