Recently, an anthraquinone-supported thiourea group linking a 1-aza-18-crown-6 macrocycle L has been the subject of extensive attention due to the perfect affinity towards metal cations. This work systematically researched the effects of different metal cations ([Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text] and [Formula: see text]) on the second-order nonlinear optical (NLO) properties of macrocycle L by density functional theory (DFT). DFT calculations revealed that the values of first hyperpolarizabilities ([Formula: see text] decrease significantly when alkaline earth metal cations ([Formula: see text] and [Formula: see text]) were injected into macrocycle L due to the smaller charge transfer (CT) transition and larger transition energy. Conversely, the variations of [Formula: see text] values in alkali metal cations ([Formula: see text] and [Formula: see text] and transition metal cations ([Formula: see text] and [Formula: see text]) derivatives are not obvious compared to the [Formula: see text] value of macrocycle L. Therefore, the NLO properties of macrocycle can be effectively regulated by alkaline earth metal cations. Furthermore, we found that the [Formula: see text] value of anion-controlled complex Na(L)(ClO4) is larger than that of L*Na+ complex because the anion [Formula: see text] improves the planarity of anthraquinone-supported thiourea group leading to the enhancement of the CT ability. In addition, the influence of frequency-dependent on the first hyperpolarizabilities is weak for the current systems. Hence, we look forward to the conception of this work will offer a fundamental guideline and reference for further research for novel NLO materials.

中文翻译：

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通过引入金属阳离子调节蒽醌负载的硫脲连接的冠醚大环的NLO响应：DFT研究

最近，连接1-aza-18-crown-6大环L的蒽醌负载的硫脲基团由于对金属阳离子的完美亲和力而受到广泛关注。本工作系统地研究了不同金属阳离子的影响（[公式：见文]、[公式：见文]、[公式：见文]、[公式：见文]、[公式：见文]和[公式：见文] text]) 用密度泛函理论 (DFT) 研究大环 L 的二阶非线性光学 (NLO) 特性。DFT 计算表明，由于较小的电荷转移（ CT) 跃迁和较大的跃迁能量。相反，[公式：4) 大于 L*Na+复杂，因为阴离子[公式：见正文]提高了蒽醌负载的硫脲基团的平面性，导致CT能力增强。此外，频率依赖性对第一超极化率的影响对于当前系统来说是微弱的。因此，我们期待这项工作的概念将为进一步研究新型 NLO 材料提供基本指导和参考。