新型大环化合物的合成及性能研究推动着超分子化学的发展。特殊极性 (大极性或小极性) 的大环化合物及其主客体复合物体系的开发是大环化学研究的重要领域。本论文工作集中于大极性的正电荷咪唑盐大环化合物及小极性的富碳大环化合物的合成及性能研究，开展了以下两部分工作： (1) 以正四价咪唑盐大环化合物14+?4PF6? (环[2](2,6-二(1H-咪唑基)吡啶[2](1,4-二亚甲基苯)六氟磷酸盐) 为主体，发展了“一锅法”多组份自组装的轮烷合成新策略。以14+?4PF6?，1,3,5-苯三甲酸阴离子物种和金属离子Ag+ 进行“一锅法”三组份自组装，在溶液和固相中均获得了金属-有机轮烷复合物。特定条件下可在溶液中定量生成 [3]轮烷结构。该 [3]轮烷对系列环境刺激 (如：离子、温度及外加小分子) 具有响应性，发生其结构的解离重组或改变轮烷内大环分子翻转运动的速率。所探究的大环围绕轮烷“轴”进行的构象翻转运动为轮烷运动的新模式。进一步利用同样的合成策略，通过金属阳离子Cd2+ 对Ag+ 的简单替换，实现了金属-有机多聚轮烷结构的构筑，证明所发展的轮烷合成新策略具有一定的普适性。 (2) 合成了系列具有CMPs (环间苯) 骨架的富碳大环化合物，并对其构象转变、分子识别性能及其主客体复合物体系的相关应用进行了深入的研究。特定条件下，通过溶液法直接合成的富碳大环 CDMB-8 (环[8](1,3-(4,6-二甲基))-苯) 具有刚性的Cs构象，而在氩气保护下进行固相高温加热可实现Cs构象到D4d构象的不可逆转变，这是通过热活化的策略实现刚性大环分子构象调控的第一个例子。热转化获得的D4d-CDMB-8有开放的“双碗式”空腔结构，使其具有了“母体”Cs-CDMB-8不具备的分子识别及应用性能。D4d-CDMB-8对全碳的富勒烯分子 (C60或C70) 展现了一定的识别能力，并利用其对不同富勒烯分子识别能力的差异性，实现了C60和C70混合物的高效分离提纯以及碳烟灰提取物中C60的提取分离。此外，利用D4d-CDMB-8、苝以及特定VOCs (挥发性有机物) (如：四氢呋喃，乙腈和甲苯等) 可构筑系列仅含碳、氢元素的主客体复合物荧光材料。VOCs蒸气环境中，这些材料可在不同时间范围内实现共晶态和混晶态之间的转变，并伴随着荧光的显著变化。利用这种时间依赖的VOCs响应荧光变色特性，首次构建了一个具有时间维度的四维信息编码系统，并实现了多个时间依赖的动态信息编码及智能读取。最后，利用 D4d-CDMB-8和曲面仅含碳、氢元素的富碳分子 (如：心环烯和 [6]CPP ([6]-环对苯))，在固相中首次构筑了仅含碳氢元素的超分子胶囊或纳米管，实现了对活性分子碘或线性分子正己烷的封装。该部分工作为小极性的富碳大环受体分子结构及性能的调控提供了新策略，且进一步发展了仅含碳、氢两种元素的主客体复合物的合成及应用研究。

Novel macrocycle study promotes the development of supramolecular chemistry. Synthesis and host-guest complexation of macrocycles with special polarity (including large or small polarity) are important fields of macrocycle chemistry. This thesis focuses on the generation and properties studies of two kinds of macrocycles, namely positive charged imidazolium macrocycles with large polarity, and all-hydrogencarbon macrocycles with small polarity: (1) We provided a facile strategy for metal-organic rotaxane using “one-pot” multi-component self-assembly from a tetracationic imidazolium macrocycle 14+?4PF6? (cyclo[2](2,6-di(1H-imidazol-1-yl)pyridine)[2](1,4-dimethylenebenzene)hexafluorophosphate). A metal-organic rotaxane complex could constract via “one-pot” three-component self-assembly of 14+?4PF6?, 1,3,5-benzenetricarboxylate anion, and silver cation (Ag+) in the solution or solid state. The present strategy allow to quantitatively generate metal-organic [3]rotaxanes under specific solution conditions. The metal-organic [3]rotaxanes can respond to a series of environmental stimulis (e.g., ions, temperature and small molecules), led to structural decomposition and recovery, or change in the rate at which the strut-threaded macrocyclic ring undergoes conformational flipping. The flipping of macrocycle around the “threaded” linear part of rotaxanes was proved to be a new movement mode of rotaxanes. Furthermore, as the demonstration of universality of the “one-pot” strategy, a self-assembled 2D metal organic rotaxane frameworks (MORFs) was obtained via easy replacing Ag+ with Cd2+. (2) A series of carbon-rich macrocycles with CMPs (Cyclo?meta?phenylenes) frameworks were synthesized, and their conformational transformation, molecule recognition performance, as well as applications of the corresponding host-guest complexs were studied in detail. A rigid Cs symmetric conformer of the carbon-rich macrocycle cyclo[8](1,3-(4,6-dimethyl)benzene (Cs-CDMB-8) could be highly selectively synthesized in acetonitrile under the specific reaction conditions. However, when Cs-CDMB-8 was subjected to high temperature heating under anaerobic conditions, a ‘new’ macrocycle with rigid D4d symmetry (D4d-CDMB-8) was obtained relies on the irreversible conversion, which is the first example to achive modulating the conformations of shape-persistent macrocycles. Futhermore, with rigid open “double bowl-shaped” conformation, the nature of D4d-CDMB-8 gives its molecules recognition and application performances that the“native”macrocycle Cs-CDMB-8 does not have. This form, D4d-CDMB-8, acts as a molecular receptor for all-carbon fullerenes (e.g., C60 and C70), and its recognition ability of different fullerene molecules was used to realize the efficient separation and purification of the mixture of C60 and C70, as well as the extraction and separation of C60 from carbon soot extract. Moreover, a series of all-hydrocarbon host-guest complex fluorescent materials were constructed by the interactions between D4d-CDMB-8 and a planar all-hydrocarbon perylene as well as specific VOC (volatile organic compound) species (e.g. tetrahydrofuran, acetonitrile and toluene). These materials can be generated on the basis of the transformations between co-crystalline states and mix-crystaline states with significant change of fluorescence proporties in different time scales by various VOC vapour treatments. This time-dependent VOC vapoluminescent was utilized to construct a four-dimensional information coding system with temporal dimension for the first time. This system allowed multiple time-dependent dynamic information coding and smart reading. Finally, the first example of supramolecular capsule or nanotube containing only hydrocarbon elements were constructed in the solid state by D4d-CDMB-8 and curved all-hydrocarbon molecules (e.g., corannulene or [6]CPP ([6]- Cyclo?para?phenylenes)). These sturctures allowed to encapsulate the molecules such as iodine or n-hexane. This part of work provides a new strategy for regulating the structures and properties of small polarity carbon-rich macrocyclic receptors, as well as developing the syntheses and applications of host-guest complexes containing only hydrocarbons.