含氧酸根阴离子是自然界中广泛存在的一类重要物质，其在生命科学，环境科学，材料科学、医药学等领域扮演着重要的角色。对于特定含氧酸根阴离子的检测、富集、捕获是目前阴离子传感器研究的重点。设计与开发新型阴离子识别传感器，是超分子化学研究的热点问题。

阴离子传感器依赖于光/电信号转导机制，即传感过程中，传感器与阴离子的结合被转化为光学或电化学信号输出的变化。其中，能使荧光开启或增强的传感机理信号易于观测，从而提高传感的灵敏度与准确性。

本论文第一部分工作将探究一种新的阴离子传感方法，即激基复合物解聚诱导荧光发射 (EDIE) 。在乙腈溶液中，新型咪唑鎓盐大环传感器 (环[1]1,4-二(1H-咪唑基)亚甲基苯[1](2,6-二胺-二吡啶)吡啶) 的六氟磷酸盐本身只有弱的荧光发射，因其在光照条件下形成无荧光发射的激基复合物，其与含氧阴离子 (如焦磷酸根、磷酸氢根等) 结合形成具有强荧光发射的大环-阴离子复合物 (0.020 mM时阴离子诱导荧光增强即可达200倍) 。这使得传感器对焦磷酸根和磷酸氢根的检测十分灵敏和有效，而该传感器对碳酸氢根的响应弱，对硫酸氢根和硝酸根的响应更弱，对卤素离子、叠氮酸根、硫氰酸根等不含氧的阴离子则无响应。该大环传感器高选择性地识别焦磷酸根和磷酸酸根的同时具有高抗干扰性，这是传感器自身缔合以及其与阴离子竞争性结合综合作用的结果。X-射线单晶衍射结构分析也支持溶液中的研究结论。

本文第二部分工作合成了系列咪唑鎓盐阴离子传感器；并从紫外光谱、荧光光谱等多种角度探讨骨架结构变化对咪唑鎓盐阴离子化学传感器形成激基复合物的影响，进而探讨结构因素在阴离子诱导激基复合物解聚产生荧光 (EDIE) 过程中的系统性规律。结果表明，随着桥联基团的改变，主体分子骨架结构得以精细调控，环张力越大，越有利于形成激基复合物。初步探究这一系列咪唑鎓盐主体与焦磷酸根或磷酸酸根的相互作用，发现结构的微调能显著改善对这两个离子荧光传感较差的选择性。

Oxoanions are important substances widely existing in nature, which plays important roles in the fields of life science, environmental science, material science, medicine and so on. The detection, enrichment and capture of specific oxoanions are the focus of anion sensing chemistry. The design and development of a new anion sensor is a hot topic in the research of supramolecular chemistry.

Oxoanion sensors rely on the light / electrical signal transduction mechanism, that is, the binding events between sensor and anion is transformed into the change of optical or electrochemical signal output. Among them, the sensing signal which can make the fluorescence on or enhanced is easy to observe, that is so-called “turn-on” fluorescent sensor. Fluorescence “turn-on” could improve the sensitivity and selsctivity of the specific sensor.

In the first part of this work, we explored a new anion sensing mechanism, namely, excimer disaggregation induced emission (EDIE). In acetonitrile solution, a new imidazolium macrocyclic sensor (cyclo[1]N²,N⁶-dimethyl-N²,N⁶-bis(6-(1H-imidazolium-1-yl)pyridin-2-yl)pyridine-2,6-diamine[1]1,4-dimethylbenzene hexafluorophosphate, 1²⁺?2PF₆^-) has weak fluorescence emission. It forms a non-emissive excimer under light condition. Addition of oxoanions (such as pyrophosphate or hydrophosphate) could disrupt the formation of excimer with strong fluorescence emission (the enhanced fluorescence of anion induced can be 200 times in 0.020 mM 1²⁺). It is sensitive and effective for the sensor to detect pyrophosphate and hydrophosphate, and to a less extent for bicarbonate. The fluorescence response is less to hydrogen sulfate and nitrate, and no response to halogen, azide, thiocyanate and other non-oxoanions. The macrocyclic sensor has high selectivity in identifying pyrophosphate and hydrophosphate with high anti-interference, which is attributed in the association of sensor and competing anions. The net results of study in solution are also supported by diffraction analysis of X-ray single crystal.

In the second part of this work, a series of imidazolium sensors were synthesized. The difference of the formation of excimer complexes mediated by change of structure on the skeleton of sensors were discussed from UV and fluorescence spectra. Then the systematic rules of the structural factors in the process of the excimer disaggregation induced emission (EDIE) were discussed. The results show that with the change of bridging group, the skeleton structure of the host molecule can be regulated. Greater ring-tension induces a more favorable excimer formation. The interaction between the imidazolium sensors and pyrophosphate or hrodrophosphate were studied. It was found that the fine-tuning of host structure could significantly improve the selectivity of these two anions fluorescence sensing process.