手性低维发光金属卤化物的制备及应用

有机-无机杂化金属卤化物材料由于其具有灵活的晶体结构、可调节的发光颜色和带隙、溶液可加工以及制备成本低廉的特点，被广泛用于太阳能电池、光电探测器、发光二极管（Light-Emitting Diode, LED）和非线性光学等诸多领域。组合不同尺寸的有机组分和多样化的无机组分，可以制备出结构多样、性质丰富的杂化金属卤化物。有机配体在调控杂化金属卤化物的结构和性质中发挥了关键作用。例如，通过调整有机配体的尺寸可以改变晶体的结构维度，而且随着结构维度的降低，材料的光致发光量子效率（Photoluminescence Quantum Yield, PLQY）逐渐提高；采用功能化的有机配体能够有针对性地设计和合成具有特定光学性质的材料；通过调控有机配体与无机组分间的氢键相互作用可以改善材料的光学性质。鉴于此，本论文以低维发光金属卤化物为研究对象，基于离子掺杂和有机配体的选择，研究了增强手性杂化金属卤化物圆偏振发光（Circularly Polarized Luminescence, CPL）的方法和提升手性杂化金属卤化物二次谐波（Second Harmonic Generation, SHG）强度的策略，揭示了手性杂化金属卤化物的晶体结构与CPL性能和SHG强度之间的关系，成功实现了兼具优异非线性和线性光学性质的手性Sb基金属卤化物的制备。主要研究内容和结果如下：

通过双配体策略，在手性0D杂化金属卤化物中实现了同时具有高PLQY和高发光不对称因子（g_lum）值的CPL。通过同时引入手性和非手性配体，成功构筑了3对对映体，包括(R/S-MBA)₂(Gua)₄(InCl₆)₂∙H₂O（MBA=α-甲基苯甲基胺，Gua=胍）、(R/S-4MBA)(Gua)₂InCl₆∙H₂O（4MBA=1-(4-甲基苯基)乙胺）和(R/S-NMBA)(Gua)₂InCl₆（NMBA=N-甲基苯乙胺）。通过掺杂Sb³⁺，这3对对映体的PLQY提升至接近100%，g_lum值高达1´10^-2。实验结果表明，非手性Gua配体不仅是这些手性杂化In-Sb氯化物结晶获得高达100%的PLQY所必需的，而且大大增强了有机配体与无机单元间的手性诱导。此外，选择不同的手性配体可以改变这些手性0D杂化金属卤化物中手性配体与无机八面体间氢键相互作用的强度，从而使其g_lum值最大化。

通过增加无机八面体的偏心畸变程度，有效地增强了手性0D杂化In-Sb氯化物的CPL。基于双配体策略、通过改变非手性配体的尺寸和Sb³⁺掺杂浓度，制备了5对对映体，包括(R/S-MBA)₂(2MA)In_0.95Sb_0.05Cl₆（2MA=二甲胺）、(R/S-MBA)₂(3MA)In_0.95Sb_0.05Cl₆（3MA=三甲胺）、(R/S-MBA)₂(3MA)In_0.79Sb_0.21Cl₆、(R/S-MBA)₂(3MA)In_0.72Sb_0.28Cl₆和(R/S-MBA)₂(3MA)In_0.59Sb_0.41Cl₆，它们的PLQY都为100%。CPL的g_lum值随着无机八面体偏心畸变增加而增加，实现了PLQY高达100%、g_lum高达3.8´10^-2的CPL性能。实验结果表明，非手性配体的类型决定无机八面体单元周围氢键的分布类型，Sb³⁺掺杂浓度决定氢键的强度。无机八面体周围不同的氢键分布类型和强度导致其具有不同程度的偏心畸变。这个研究揭示了手性0D杂化In-Sb氯化物发光材料的结构与CPL性能间的关系，为设计高g_lum值的CPL发光材料提供了指导。

揭示了手性0D Sb基杂化金属卤化物晶体结构与SHG强度间的关系。基于双配体策略，通过改变卤素（Cl、Br）的种类制备了3种不同偏心畸变程度的手性Sb基金属卤化物，研究了SHG强度与金属卤化物结构间的关系。研究发现SHG强度和响应范围与金属卤化物材料中无机八面体的偏心畸变程度成正比，具有最大偏心畸变程度的(R-MBA)₂IASbCl₆（R-SbCl₆，IA=咪唑）SHG强度是Y-cut石英晶体的143倍，此外，在R-SbCl₆中实现了g_lum值高达3.8´10^-2的CPL性能。在R-SbCl₆中成功实现了兼具优异非线性和线性光学性质，将会扩展金属卤化物发光材料在非线性和线性光学领域的应用。

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