两种手性零维杂化金属卤化物的制备与光学性能研究

手性零维杂化金属卤化物由于其出色的光学性能，在圆偏振发光（CPL） 应用领域具有无限的潜力。光致发光量子产率（PLQY）以及发光不对称因 子（glum）是衡量手性材料 CPL 性能的重要标准。尽管手性零维杂化金属卤 化物的研究已经取得一定进展，但同时具备高 PLQY 和高 glum 值的材料的研 究仍处于初始阶段。本文以开发兼具高 PLQY 和高 glum 值的新型手性零维杂 化金属卤化物为目标，制备了铜和稀土基手性杂化金属卤化物，并对其结构 和光学性能进行了深入研究，具体工作如下： 采用冷却结晶法，以内消旋的 1,2-环己二胺（DACH）为配体制备了不 发光材料(18C6@meso-DACH)2Cu2I6（18C6=18-冠醚-6，meso-DACH=顺式1,2-环己二胺）。而使用具有手性的 DACH 配体，则会诱导无机金属卤化物 单元对称性破缺进而发生结构重组，形成具有明亮黄光发射的手性零维 Cu 基杂化金属卤化物(18C6@S/R-DACH@18C6)Cu4I6，该材料具有接近 100%的 PLQY，其 glum 达到了±0.005。而使用外消旋的配体导致材料对称性升高，所 制备的(18C6@rac-DACH)CuI3 仍为不发光材料。结构分析与理论计算的结果 表明，手性的[Cu4I6] 2-团簇，其形成能低于非手性的[CuI3] 2-和[Cu2I6] 4-，而非 手性配体的致密堆积不利于[Cu4I6] 2-团簇的生长，因此大体积的[Cu4I6] 2-仅在 手性分子非致密堆积的结构中形成。本工作一方面揭示了非中心堆积对金属 卤化物结构和性质差异的影响，同时利用手性配体诱导材料结构重组的特点， 成功地实现了材料在手性识别与智能防伪领域的应用。 采用溶剂挥发法，合成了具有稀土窄带发射特点的手性零维 Tb/Eu 基杂 化金属卤化物(S/R-3-MOR)3TbCl6 与(S/R-3-MOR)3EuCl6（S/R-3-MOR=S/R-3- 甲基吗啉），在 365 nm 的紫外光激发下分别呈现明亮的绿色/红色窄带发射， 符合 Tb/Eu 稀土的离子发射特征。基于 Tb/Eu 的手性材料展现出优异的光学 性能，其 PLQY 分别为 91.2%和 52.0%，glum 值分别达到±0.006，±0.009。同 时，这两种材料表现出反热猝灭效应，表明了其在具有高效圆偏振发射的发 光二极管领域的应用潜力。

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