刚性萘基大环主体的设计合成及其分子识别研究

设计和构建具有特定结构和性质的新型大环主体一直是超分子化学领域中备受关注的研究课题。刚性骨架在定义大环主体的空腔性质方面具有一定的结构优势，然而如何合理利用刚性骨架的结构特征并构筑具有特定性质的大环主体一直是超分子领域的难题之一。本篇论文围绕刚性弧形骨架展开研究，合成了一类新型大环主体分子，并详细研究了其构型和构象变化、分子识别及其在手性传感等方面的应用。此外，利用不同刚性骨架对大环结构的限制，精准调控了内修饰空腔结合位点的距离，进一步实现了大环主体在水中对特定客体的精准识别。

（1）目前报道的大环芳烃多以平面芳香环作为成环构建基元，过多引入亚甲基通常会导致大环结构的高柔性。本论文利用刚性桥联双萘构筑了一类亚甲基桥联萘管，并探究了侧链长度对大环构型和构象的影响。其中三元萘管具有刚性规整的深穴空腔，而四元大环根据烷氧基侧链的长度分别具有伪双空腔构象或自填充构象。

（2）研究了亚甲基桥联萘管的分子识别性质。三元萘管具有优异的分子识别能力，对有机阳离子的结合亲合力高达10⁸ L/mol，明显优于结构相似但更具柔性的棱芳烃。这展现了刚性规整空腔在分子识别领域的独特优势。四元萘管则可以1:1结合小尺寸的阳离子客体。此外，亚甲基桥联萘管可以作为手性传感器实现对手性阳离子客体的手性传感。三元萘管和四元萘管在手性传感方面的能力相互补充，可以分别适用于对不同尺寸的手性阳离子客体的手性传感及ee值确认（误差小于5%）。

（3）利用刚性桥联双萘和弯曲蒽二聚两种不同的刚性弧形骨架，共同构筑了一类新型内修饰酰胺杂管。两种刚性骨架具有不同的开口大小和宽度，可以细微调整内修饰空腔结合位点之间的距离，从而实现了对特定客体（苯并二氢吡喃–4–酮）的选择性识别。酰胺杂管对结构相似的客体的选择性最高可达210倍，这几乎媲美生物受体的识别选择性。

本篇论文丰富了超分子化学的大环主体工具箱，展示了刚性弧形骨架在设计新型大环主体分子和调控内修饰空腔识别性质方面的优势及重要性，为新型大环主体分子的设计与合成提供了新思路。

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