Unraveling the Substituent-Controlled Fluorescence Modulation in One-Dimensional Cd-Based Coordination Polymers: A Structure–Property Relationship Study

The substituent engineering strategy has emerged as a
powerful
tool for precise modulation of the structure–property relationships
in coordination polymers (CPs), yet the rational design of isostructural
CPs with tunable dual-channel fluorescence and integrated stimulus-responsive
behaviors remains a compelling challenge. Herein, three isostructural,
one-dimensional Cd-based CPs (1–3) were rationally designed and hydrothermally synthesized via systematic
substituent modification. Notably, the solid-state fluorescence of 1–3 is precisely regulated by the electronic
and steric effects of substituents, enabling dual-channel emission
encompassing ligand-centered monomer fluorescence and excimer-derived
fluorescence. Furthermore, systematic investigations reveal that these
CPs exhibit distinct thermoresponsive and mechanoresponsive fluorescence
behaviors, which are closely correlated with substituent-induced structural
subtlety. This work not only demonstrates the efficacy of substituent
engineering in tailoring dual-channel fluorescence within isostructural
CPs but also provides insights into the design of multifunctional,
stimulus-responsive fluorescent materials for potential applications
in sensors and optoelectronics.

取代基工程策略已成为精准调控配位聚合物（coordination polymers, CPs）构效关系的强大工具，但合理设计具备可调谐双通道荧光与集成刺激响应行为的同构配位聚合物，仍是一项极具吸引力的研究挑战。本研究通过系统性取代基修饰，理性设计并水热合成了三例同构的一维镉基配位聚合物（1~3）。值得注意的是，1~3的固态荧光可通过取代基的电子效应与位阻效应实现精准调控，呈现涵盖配体中心单体荧光与激基缔合物衍生荧光的双通道发射。进一步系统研究表明，此类配位聚合物展现出截然不同的热响应与机械响应荧光行为，且与取代基诱导的结构细微差异密切相关。本工作不仅证实了取代基工程在调控同构配位聚合物双通道荧光方面的有效性，还为设计多功能刺激响应荧光材料提供了思路，有望应用于传感器与光电子器件领域。