基于配位聚合物的合成后修饰策略：从结构设计到性能调控

Post-Synthetic Modification Strategies Based on Coordination Polymers: From Structural Design to Property Modulation

摘要: 合成后修饰策略为克服传统一锅法在平衡配位聚合物稳定性与引入特定功能之间的矛盾提供了有效途径。该策略通过分步方式，将稀土离子(Ln³⁺)定向引入预先构建的、结构稳定的配位聚合物的孔道或特定位点，从而实现对材料发光性能的精准调控。本综述指出，成功的合成后修饰取决于配位聚合物结构的合理设计：贯通且表面化学适宜的孔道为Ln³⁺提供传质通道；配位不饱和位点确保其稳定结合；而配体三重态能级与Ln³⁺激发态的匹配则确保高效的能量传递。基于此，体系中配体的宽带发射与Ln³⁺的特征发射天然共存，构成了理想的双发射体系，为构建自校准比率荧光传感平台奠定了光物理基础。分析物可通过竞争配位、能量转移等相互作用，特异性调控某一发光通道的强度，进而引起发光强度比的规律变化，以此实现对抗生素、金属离子及生物小分子的高灵敏、高选择性检测。该策略不仅拓宽了比率传感在环境与生物分析中的应用范围，也为开发温度、pH等物理性质传感材料提供了新思路。今后的研究应聚焦于Ln³⁺局部化学环境与能量传递路径的原位表征、高稳定性配合物材料的设计以及制备便携式检测设备，以推动其在实际检测中的应用。

Abstract: The post-synthetic modification (PSM) strategy offers an effective approach to overcoming the inherent compromise between structural stability and specific functionality in traditional one-pot synthesis of coordination polymers. This stepwise method involves the directional introduction of lanthanide ions (Ln³⁺) into the pores or specific sites of pre-constructed, structurally stable coordination polymers (CPs), enabling precise control over the luminescence properties of the material. This review emphasizes that successful functionalization is fundamentally rooted in the rational design of the host framework: interconnected pores with suitable surface chemistry provide mass transport channels for Ln³⁺; coordinatively unsaturated sites ensure stable anchoring; and a matched energy level between the ligand triplet state and the Ln³⁺ excited state supports efficient energy transfer via the “antenna effect.” Consequently, the broad ligand-based emission and the characteristic sharp emission of Ln³⁺ coexist naturally within the system, forming an ideal dual-emission system that lays the photophysical foundation for constructing self-calibrating ratiometric fluorescent sensing fluorescent sensing platforms. Analytes can selectively modulate the intensity of one emission channel through interactions such as competitive coordination or energy transfer, leading to predictable changes in the emission intensity ratio. This enables highly sensitive and selective detection of antibiotics, metal ions, and small biomolecules. This strategy not only broadens the application scope of ratiometric fluorescent sensing sensing in environmental and biological analysis but also provides new avenues for developing sensing materials for physical parameters such as temperature and pH. Future research should focus on in situ characterization of the local chemical environment surrounding Ln³⁺ ions and their associated energy transfer pathways, as well as the design of highly stable host materials and the development of portable detection devices, to advance practical applications in real-world sensing.