[2,2]对二苯环蕃(PCP)由两个桥联的苯环组成，独特的物理结构导致了它自身优异的光电特性，其作为手性基元已广泛应用于不对称合成、超分子组装、聚合物化学和材料科学等诸多领域。[2,2]PCP多模式的取代位点致使其产生独特的平面手性，将之与多种荧光基团结合，可构筑具有优异性能的手性发光分子。在本文中，我们将[2,2]PCP与双吡啶四苯乙烯、芘基、自由基结合，设计了一系列基于[2,2]PCP的新型衍生物，探索了这一系列衍生物的光物理性质及自组装性能，并取得了以下成果：

1. 我们利用金属协同配位作用将伪邻位[2,2]PCP双铂配体（rac/Rp-PCP）、四苯乙烯（TPy）配体结合构筑了两种新型双螺旋结构（(Rp,Rp-)PCP-TPy1/2）。通过核磁、质谱、理论计算等多种表征手段对双螺旋结构进行了确认。区别于传统双螺旋结构，该双螺旋结构由[2,2]PCP手性中心主导，而非N-Pt金属中心控制。在四氢呋喃/水(1:9,v/v)混合溶液中，该双螺旋结构展现出优秀的聚集诱导发光（AIE）性能。(Rp,Rp-)PCP-TPy1/2在混合溶液中可组装为球形聚集体，我们以这些球形聚集体作为能量给体，曙红（EsY）或尼罗红（NiR）作为能量受体构筑了一系列单步、连续人工光捕获系统（ALHSs）。由PCP-TPy1、EsY、NiR所构筑的连续能量传递系统的传递效率高达89.3%。此外，该种双螺旋结构还可制备发光器件，PCP-TPy1的PMMA薄膜可掺杂0.075% NiR制备白光薄膜，(Rp,Rp-)PCP-TPy2的固体粉末可用作蓝色LED灯泡的助剂制备白光。本研究为新型双螺旋结构的制备提供了一种通用的方法，并探索了其在荧光材料中的应用，对未来双螺旋结构的构建及应用具有重要的指导意义。

2. 我们利用[2,2]PCP的多取代位点，合理控制芘基与[2,2]PCP的连接方式，设计并合成了一系列芘基[2,2]PCP衍生物。这些芘基[2,2]PCP衍生物具有不同的晶体堆积模式。pm/po-PCP-P1中存在三键，分子间空间位阻较小，芘基相互可发生较强的π-π堆积相互作用。反之，单键相连的pm/po-PCP-P2空间位阻较大，π-π堆积作用较弱。π-π堆积差异导致这些分子具有不同的准分子发光以及荧光量子产率。此外，由于结构的差异，这些芘基[2,2]PCP衍生物具有相同手性核心也会表现出相反的CD以及CPL信号。芘基[2,2]PCP衍生物在固态及PMMA薄膜中由于堆积差异也导致其荧光发射存在差异。这四种芘基[2,2]衍生物还可与苝酰亚胺（PDI）相互作用，构建一步能量转移体系并产生近白色荧光。

3. 我们将[2,2]PCP骨架与2,4,6-三氯苯基（TTM）自由基、咔唑相结合。[2,2]PCP骨架为分子提供手性基元，咔唑可稳定自由基的光学性能。我们尝试了多种合成路线，最终获得了三者相结合的分子。咔唑位于结构中心，TTM自由基与其直连，[2,2]PCP位于咔唑侧边。通过核磁氢谱、质谱对结构进行了确认。PCP-Cz在正己烷中具有红色荧光，荧光量子产率可达32.2%，是一种较为优异荧光发射体。我们成功对这两种自由基进行了拆分并研究了其手性光谱性质。

[2.2]Paracyclophane (PCP) consists of two brided benzene rings, their unique physical structure results in their own excellent photoelectric properties. Recently, [2.2]Paracyclophane (PCP)has been widely utilized as chiral units for diverse applications from asymmetric synthesis to supramolecular assembly, polymer chemistry and material science. The multi-substitution positions of [2,2]PCP result in its unique planar chirality, which can be combined with a variety of fluorophores to construct chiral luminescent molecules with excellent properties. In this paper, we combined [2,2]PCP with dipyridine tetraphene, pyrene group and free radical to design a series of novel derivatives based on [2,2]PCP, explored the photophysical properties and self-assembly properties of these derivatives. The research content is delineated as follows:

1. Two double helicates ((Rp,Rp-)PCP-TPy1/2) and their chiral counterparts were designed and synthesized using pseudo-ortho- (po-) [2,2]PCP diplatinum(II) complex (rac/Rp-PCP) and dipyridyl TPE ligands through metal-coordination interaction. These double helicates were all confirmed by various analytic techniques, including ¹H NMR, electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS), theoretical calculation, and so on. Different from the traditional double helicates, these helicates are dominated by 3D planar chiral [2.2]PCP units, but are not dominated by the Pt-N metal-coordination centers. All double helicates exhibit significant aggregation-induced emission in tetrahydrofuran/water (1:9, v/v) solvent. The aggregated double helicates can be used to construct one-step or sequential ALHSs with fluorescent dyes Eosin Y (EsY) and Nile red (NiR) with the energy transfer efficiency up to 89.3%. In addition, the two double helicates also can be used to produce light-emitting devices. The PMMA film of PCP-TPy1 shows white-light emission when doped 0.075% NiR, the solid of double helicates (Rp,Rp-)PCP-TPy2 can be used as the additive of a blue LED bulb to achieve white-light emission. In this work, we provided a general method for the preparation of novel double helicates and explored their applications in fluorescent materials, which will promote future construction and application of helicates as emissive devices.

2. A series of pyrene-based [2,2]PCP derivatives were designed and synthesized by considering the substitution positions and connection patterns of [2,2]PCP cores. These pyrene-based [2,2]PCP derivatives exhibited diverse structures and crystal packings in the solid phases. The presence of a triple bond in pm/po-PCP-P1 results in less steric hindrance between molecules, thereby promoting a strong π-π stacking interaction among the pyrene units at the molecular level. In contrast, pm/po-PCP-P2 without a triple bond spacer display significant intermolecular steric hindrance and consequently lead to a weak π-π stacking interaction among the pyrene units. These variations in chemical structures among these pyrene-based [2,2]PCP derivatives consequently result in monomer and excimer emissions with the different fluorescence quantum yields. Additionally, due to structural differences, these pyrene [2,2]PCP derivatives exhibit opposite CD and CPL signals despite having the same chiral core. These pyrene-based [2,2]PCP derivatives also exhibit diverse properties in the solid state and PMMA films due to their different packings. Furthermore, Moreover, these pyrene-based [2,2]PCP derivatives also can interact with perylene diimide through π-π interactions, leading to near-white fluorescence.

3. We used the multiple substitution sites of [2,2]PCP skeleton and combined them with TTM radical and carbazole. We utilized the multiple substitution sites of the [2,2]PCP skeleton and integrated them with TTM radical and carbazole. The [2,2]PCP skeleton imparts unique planar chirality to the molecule, and the addition of carbazole further enhances the stability of the radical's optical properties. We tried a variety of synthetic routes, and finally obtained a molecule with [2,2]PCP, carbazole and TTM radical. Carbazole is located in the center of the structure, with the TTM radical directly connected to it, and [2,2]PCP situated on the side of carbazole. The molecular structures were all confirmed by ¹H NMR and electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS). The radical PCP-Cz exhibits red fluorescence in n-hexane, and its fluorescence quantum yield is as high as 32.2%, making it an excellent emitter of fluorescence. The chiral structure of PCP-Cz is obtained by HPLC, but the CD signal is weak because the chiral center is far from the radical. Compound 2PCP-Cz may contains one pair of enantiomers and one mesomer, making it difficult to separate. Although the chiral signal of the chiral luminescent radical obtained in this part of work is weak, we have explored its synthesis route, laying a foundation for the synthesis of chiral luminescent radicals with excellent properties.