构建具有新颖结构和优异性能的大环宿主已经成为超分子化学中的一项热门课题。为了获得具有更加独特结构和性质的大环主体，科学家常常在大环中引入不同的构建基元，以此来改变大环的性质，拓宽其应用领域。因此，设计与合成具有三维立体结构与手性性质的大环主体是十分有必要的。本论文中，我们选择具有三维刚性结构的三碟烯作为构建模块，使其分别与柱芳烃和环对苯撑结合，构建了几种刚性的新型大环主体。具体研究内容如下：

1. 基于三碟烯（TPs），设计合成了一种具有固定构象的新型三碟烯基柱[6]芳烃（TP[6]）。单晶结构表明，TP[6]有着近似于六边形的螺旋富电子腔，赋予了大环封装缺电子客体的能力。通过化学拆分法，成功实现了手性三碟烯的拆分，并分别由手性三碟烯出发成功合成一对手性TP[6]。核磁实验和等温滴定量热法研究表明，手性TP[6]对于四对含有三甲基氨基的手性客体表现出对映选择性，这意味着TP[6]在对映选择性识别领域具有潜在应用。

2. 以三碟烯为连接体，通过环缩合策略在三碟烯叶片上选择性连接不同个数的 [10] 环对苯撑 （[10]CPP），成功构建了三种 [10]CPP衍生大环（TP- [10]CPP-1、TP- [10]CPP-2和TP- [10]CPP-3）。光物理性质测试表明，三种大环的最大吸收波长基本一致，但荧光发射峰却随着分子内 [10]CPP数目的增多而发生红移，三者都有着较大的斯托克斯位移，其荧光量子产率高达66.0 %，荧光寿命长达13.92 ns。值得注意的是，根据紫外工作曲线可知，大环TP- [10]CPP-1与C₆₀能够按照1:1的比例络合，络合常数Ka = 3.9 × 10⁵ M^-1；TP- [10]CPP-2与C₆₀以1:2比例络合，络合常数Ka₁ = 3.6 × 10⁵ M^-1，Ka₂ = 6.4 × 10⁵ M^-1；意料之外的是，具有三个 [10]CPP的大环TP- [10]CPP-3与C₆₀形成的是1:2络合物，而非期望的1:3络合物，非线性拟合得络合常数Ka₁ = 4.0 × 10⁵ M^-1，Ka₂ = 2.5 × 10⁵ M^-1。

Construction of macrocyclic hosts with novel structures and excellent properties has emerged as an intriguing undertaking in supramolecular chemistry for the past few years. In order to obtain macrocyclic hosts with more unique structures and properties, scientists often introduce different building blocks into macrocyclic hosts, so as to change the properties of macrocyclic hosts and broaden their application. Therefore, it is necessary to design and synthesize macrocyclic hosts with three-dimensional structure and chiral properties. In this thesis, we select triptycene which possesses three-dimensional rigid structure as the building block, and combine it with pillararene and cycloparaphenylenes respectively to construct novel macrocyclic hosts with rigid structure. The specific research contents are as follows:

1. Based on triptycenes (TPs), a shape-persistent triptycene-derived pillar[6]arene (TP[6]) was designed and synthesized. The single crystal structure analysis revealed that TP[6] adopts a hexagonal structure, featuring a helical and electron-rich cavity capable of encapsulating electron-deficient guests. The chiral triptycenes were successfully separated by chemical resolution method, and a pair of chiral TP[6] were successfully synthesized from the chiral triptycenes. The ¹H NMR and isothermal titration calorimetry investigations demonstrated that chiral TP[6] exhibited enantioselectivity toward four pairs of chiral guests containing a trimethyl amino group, implying a significant promising application in area of enantioselective recognition.

2. Three kinds of [10]CPP-derived macrocyclic hosts (TP- [10]CPP-1、TP- [10]CPP-2 and TP- [10]CPP-3) were successfully constructed by selective connection [10] cycloparaphenylenes ([10] CPPs) on the blades of triptycenes respectively by ring condensation strategy. Photophysical property investigations show that the maximum absorption wavelengths of the three macrocycles is approximately identical, but the fluorescence emission peaks redshift as the number of [10] CPPs increases within the molecules. All three macrocycles have large Stokes shifts, fluorescence quantum yields of up to 66.0%, and fluorescence lifetimes of up to 13.92 ns. It is worth noting that according to the Job plot based on UV-vis, TP- [10]CPP-1 can complex with C₆₀ at the ratio of 1:1 and the complexation constant Ka = 3.9 × 10⁵ M^-1. TP- [10]CPP-2 can complex with C₆₀ at the ratio of 1:2 and the complexation constant Ka₁ = 3.6 × 10⁵ M^-1，Ka₂ = 6.4 × 10⁵ M^-1. Unexpectedly, TP- [10]CPP-3 with three [10] CPPs can only form 1:2 complex with C₆₀, not 1:3. The complex constant Ka₁ = 4.0 × 10⁵ M^-1，Ka₂ = 2.5 × 10⁵ M^-1.