新颖有机大环与超分子化学

The design and synthesis of novel and functional macrocycles have always been one of the central focuses of the cutting-edge research disciplines of organic chemistry. The emergence of “privileged” macrocyclic host molecules provides one of the driving forces to promote the development of supramolecular chemistry. Very recently, corona[n]arenes, a new type of macrocyclic host molecules which are composed of para-(het)arylenes and heteroatoms in an alternative manner, have been proposed. This NSFC key project aims at, first of all, the development of highly efficient and practical methods for the synthesis of diverse corona[n]arenes. Secondly, the macrocyclic structures and particularly the effect of the linking heteroatoms and their conjugation with adjacent aromatic rings on the macrocyclic structures will be explicitly elucidated. The fine tuning of macrocyclic conformation, cavity and property of corona[n]arenes will be investigated. In addition, a thorough and systematic study on molecular recognition towards various electron-neutral and charged guest species will be executed with the emphasis on the comprehension of the nature of the non-covalent bond interactions between corona[n]arene hosts and guests. The investigation on structure-property correlation of macrocyclic hosts will be equally addressed. Finally, based on the acquired knowledge of the host-guest chemistry of corona[n]arenes, we will strive to explore assembled systems that act as carries and channels to transport ions and molecules. The ultimate goal of the project is to establish and develop new and unique macrocyclic and supramolecular chemistry of corona[n]arenes, promoting the further development of supramolecular chemistry.

新型和功能化的人工合成大环分子一直是有机化学的核心和前沿研究内容之一，全新和多功能的“优势”大环主体分子的产生对推动有机超分子化学的发展发挥了重要作用。最近，我们设计了一类由杂原子和对位取代芳（杂）环相连而组成的全新大环主体分子—冠芳烃。本重点项目拟深入和系统研究（1）冠芳烃的高效和实用化的合成方法学，合成具有丰富分子多样性的冠芳烃化合物；（2）认识冠芳烃大环分子结构特征，揭示桥连杂原子性质以及杂原子与芳（杂）环间相互作用对冠芳烃结构的影响规律，实现冠芳烃大环分子构象、空腔和理化性能的调控；（3）开拓冠芳烃对中性分子、阳离子、阴离子的分子识别性能，阐明主-客体间非共价作用的本质，建立冠芳烃结构与分子识别性质的关系；（4）尝试基于主-客体作用的分子组装，构建冠芳烃大环的超分子输运和分子通道体系。本项目旨在建立和发展具有我们自己特色的新型功能化冠芳烃大环与超分子化学体系，推动有机超分子的发展。

新型和功能化的人工合成大环分子一直是有机化学的核心和前沿研究内容之一，全新和多功能的“优势”大环主体分子的产生对推动有机超分子化学的发展发挥了重要作用。本重点项目建立、发展和丰富了具有特色的大环与超分子化学体系：发展了我们自己建立的冠芳烃、同冠芳烃、异冠芳烃和杂杯芳烃的合成方法，获得了多种新颖的大环化合物，并阐明了大环构象结构和影响因素；揭示了阴离子识别中的多重阴离子-π协同效应、相互依存的多重阴离子-π与多重非经典氢键的协同增强效应，总结了所合成的大环主体分子的分子识别性能和规律；以大环分子为平台，揭示了高价芳基铜的反应性质和铜盐催化的芳香碳-氢键与各类有机硼酸的交叉偶联反应以及与自由基的交叉偶联反应催化反应机理。此外，我们还建立了从雷锁芳烃经“跨湾构桥”策略合成环带烃的方法，合成了具有不同直径尺寸、不同形状、含有不同官能团和杂原子的锯齿型环带烃化合物，初步展示了具有圆台空腔结构的环带烃对有机小分子的选择性识别，为全面建立和发展全新的锯齿型环带烃的大环与超分子化学奠定了良好的基础。