功能导向三苯三戊并烯衍生物的设计合成及结构性能研究

Tribenzotriquinacene (TBTQ) forms a unique conformationally rigid, and highly C3-symmetrical, concave-convex shaped structural motif consisting of three mutually fused indane units. Owing to the particular architecture and the high reactive activity of its molecular framework, TBTQ derivatives were considered to be the optimal building blocks to construct the materials with novel structure and predictable function. TBTQ-based intrinsic microporositys and TBTQ receptors for C60 fullerene rotors have gained tremendous advantage and interest in the fileds of material science and supramolecular chemistry. The scarcity of the TBTQ sample had hampered a thorough functional property evaluation of these fascinating molecules. It is deeply pivotal and urgency for the design and high efficient synthesis of TBTQ derivatives, and exploration of their functional properties and applications. .Based on the previous work, this research proposal focuses attention on the study of synthesis and function of TBTQ derivatives. Thus, TBTQ-trimers will be designed and synthesized, with novel water wheel-like (on Yellow River) structure, and promised to regulate the scaffold for the potential applications in nano-scale machines or motors. Moreover, TBTQ-tetramers with water wave-like structure regarded as potential organic materials will be synthesized. Then the synthesis and property exploration of non-planar graphene type TBTQ derivative is another goal, we hope to get the better semiconductor material to apply to the electricity. This proposal seeks to synthesize TBTQ-based cryptophanes or hemicryptophanes possessing pronounced cavity by hydrogen bonding, coordination bonding, and dynamic covalent bonding, and to investigate their ability as the hosts towards to receptors, drug deliveries, and molecular catalysts. The proposal also intends to synthesize the novel TBTQ-based crown ethers and investigate their potential application in host-guest chemistry, and to explore the TBTQ-based supramolecular organic framework by self-assembly as well as the application of chiral TBTQ-building block. .It is believed that through this study, new TBTQ derivatives with novel function will be created, the relationship of structure and function will be revealed, and may lay a useful foundation for the TBTQ chemistry development in the material science and supramolecular chemistry.

三苯三戊并烯(tribenzotriquinacene,简称TBTQ)具C3对称凹凸骨架,反应活性高,是构筑新颖结构并具特定功能物质的优良单体,以它制备的微孔聚合物、分子机器等在材料及超分子化学领域展现出极大优势。然而受TBTQ种类和数量的限制,其性能研究进展较为缓慢,亟需设计和高效合成TBTQ衍生物深化其功能及应用研究。本项目将在前期研究工作基础上,合成TBTQ三聚体,调控这类新型分子机器的运动；制备TBTQ四聚体用作新型有机材料；合成TBTQ非平面类石墨烯,研究其半导体增强及电磁性能；通过配位键、氢键、动态共价键自组装构筑TBTQ(半)穴番,应用于分子或离子识别及超分子催化剂；合成TBTQ冠醚应用于主客体化学；拓展TBTQ超分子网络体系及手性TBTQ的应用。通过研究揭示TBTQ结构与性能的关系,为进一步功能优化与分子设计合成提供新思路,推进TBTQ在材料及超分子化学领域研究的快速发展。

三苯三戊并烯(tribenzotriquinacene,简称TBTQ)具C3对称凹凸骨架结构赋予其特殊的性质，是构筑新颖结构并具特定功能物质的优良基元。TBTQ衍生物蕴含着有待发现的新性质和功能。本项目旨在解决高效制备TBTQ新骨架物质，拓展它们在合成化学、超分子化学、材料科学及其相关学科的应用等关键科学问题，重点研究了功能导向TBTQ新骨架物质的设计、高效精准合成及其性能。. 项目拓展了对TBTQ芳基外围单、双、三、全取代可控衍生化的方法，解决了C1与C3对称TBTQ衍生物的分离、TBTQ固有手性对映体的光学拆分等难题。设计合成的TBTQ冠醚能够选择性识别铵离子，TBTQ-二苯并-24-冠醚-8选择性地识别1,1'-二甲基-4,4'-联吡啶六氟磷酸盐，在百草枯残留检测等方面具有潜在的应用前景。TBTQ-苯并-21-冠醚-7选择性地识别二丁基铵六氟磷酸盐，而与含芳香体系的铵离子无相互作用，为TBTQ冠醚的主客体化学研究增添了新内容。全取代喹啉氧甲基-TBTQ衍生物能选择性识别银离子的研究，为深化其主客体化学及在化学传感器中的应用奠定了基础。项目成功制备了2-氨基-3-溴-TBTQ外消旋体，通过拆分得到了光学纯(−)-(M)-或(+)-(P)-对映体，并以此为原料拓展至syn-双TBTQ-吡嗪的可控精准构筑。2-氨基-3-硝基-TBTQ和2-氨基-3-羧基-TBTQ外消旋体的光学拆分也已实现。以上研究揭示了TBTQ结构与性能的关系，为TBTQ多聚体的制备，以及功能优化与分子设计合成提供了新思路，丰富了功能分子的合成及超分子化学的内容，拓展了合成化学与材料科学等相关学科的交叉融合，对增强我国新材料开发自主创新能力，强化合成化学人才队伍培养均具有重要意义。