Diradical Character and Second Hyperpolarizability of Alkaline Earth Metal Inverse Sandwich Complexes Involving Cyclopentadienyl and Cyclooctatetraene Ligands,European Journal of Inorganic Chemistry

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Diradical Character and Second Hyperpolarizability of Alkaline Earth Metal Inverse Sandwich Complexes Involving Cyclopentadienyl and Cyclooctatetraene Ligands
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2018-05-06 , DOI: 10.1002/ejic.201800267
Shota Takamuku ₁ , Masayoshi Nakano _{1,

2,

3}

Affiliation

Using strong‐correlated quantum chemical calculations, we have revealed the relationship between diradical character y and second hyperpolarizability γ [third‐order nonlinear optical (NLO) property] in alkaline earth metal inverse sandwich complexes, which have Mg or Ca atoms as an alkaline earth metal and a four‐ or eight‐membered ring as an organic ligand (4‐Mg, 4‐Ca, 8‐Mg, and 8‐Ca). Through detailed analysis of diradical character with the valence configuration interaction (VCI) model, we have found that the higher period metal leads to a larger metal–metal distance with larger y value 0.8–0.9, while a larger ring size of organic ligand leads to smaller diradical character values due to the larger transfer integral (smaller distance) between metals. These features are explained by orbital diagrams and VCI analysis. Indeed, it is found that 8‐Ca has the largest γ value, which is 4.94 times as large as that of the system with the smallest γ value (8‐Mg). From these results, we obtain a design guideline for efficient third‐order NLO systems based on alkaline earth metal inverse sandwich complexes: a combination of alkaline earth metal with a higher period number and larger organic antiaromatic (4nπ) ring tends to enhance the γ value due to the larger metal–metal distance with keeping an intermediate y value.

中文翻译：

涉及环戊二烯基和环辛酸酯四烯配体的碱土金属反三明治复合物的双自由基特征和第二超极化性

使用强相关的量子化学计算，我们揭示了碱金属金属逆三明治复合物（以Mg或Ca原子为碱土）中的双自由基特性y与第二超极化率γ [三阶非线性光学（NLO）性质]之间的关系。金属和四元或八元环作为有机配体（4 Mg，4 Ca，8 Mg和8 Ca）。通过对价基相互作用（VCI）模型的双自由基特征进行详细分析，我们发现，较高周期的金属导致较大的金属-金属距离，且y值0.8-0.9，而较大的有机配体环尺寸会导致较小的双自由基特征值，这是由于金属之间的转移积分较大（距离较小）。这些功能通过轨道图和VCI分析进行解释。实际上，已发现8-Ca具有最大的γ值，这是具有最小γ值的系统（8-Mg）的4.94倍。从这些结果，我们得到基于碱土金属逆夹心复合物用于高效三阶非线性光学系统设计准则：碱土金属的具有较高周期数和更大的有机反芳香（4组合Ñ π）环趋向于提升γ由于较大的金属与金属之间的距离并保持中间y值而导致该值变大。

更新日期：2018-05-06

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