本项目提出基于单体结构预组织构筑环状、柱状、二维及三维有机有序空穴组装体。通过氢键等诱导单体形成特定构象，以实现结合作用的加合性和协同性，以高效构筑大环。利用大环结构在膜内堆积形成通道，实现跨膜输送。设计刚性平面三角型和正方形单体，分别引入三个或四个紫精或四硫富瓦烯（TTF）片段。还原紫精或氧化TTF为正离子自由基，通过堆积作用形成正离子自由基二聚体，从而构筑二维蜂窝型和方格形组装体。在四面体型刚性骨架上引入紫精或TTF等片段，同样基于自由基二聚体模块，构筑金刚石型的三维有机有序空穴组装体。通过葫芦脲[8](CB[8])等的主体络合增强作用提高二维和三维组装体的稳定性。通过CB[8]对紫精和TTF络合物的包结作用构筑类似二维和三维组装体。探索正离子型三维组装体作为“超分子海绵”吸收负离子型分子和聚电解质及核酸的功能，探索新的组装体在控制电子转移和能量传递及促进光催化反应方面的功能。

This project focuses on the controlled self-assembly of cyclic, tubular, 2D and 3D porous organic supramolecular architectures. Non-covalent forces (mainly hydrogen bonding) will be utilized to induce rationally designed building blocks to adopt specific conformation or orientation to achieve multivalent and cooperative binding. New helical and macrocyclic systems will be further exploited to stack in membranes to form column-styled architectures, which will be investigated as transmembrane channels for biologically active species. Rigid planar triangular and square building blocks, which bear three or four viologen or tetrathiafulvalene (TTF) units, will be synthesized. The viologen and TTF units will be reduced or oxidized to their monocationic radicals, respectively. The related stable radical dimers will be used to drive the building blocks to generate 2D honeycomb- and square-styled architectures. Rigid tetrahedron-styled building blocks, which bear four viologen or TTF units, will also be prepared. These monomers will be used to assemble 3D ordered porous architectures. Curcubituril[8] will be further used to enhance the stability of the 2D and 3D architectures by complexing the radical dimers and also to assemble other similar porous architectures by complexing the 1:1 complex of viologen and TTF. The function of the cationic 3D porous architectures as "supramolecular sponges" in absorbing anionic conjugated molecules, polyelectrolytes and nucleic acids will be investigated. The controlled electron and energy transfer between the assembled architectures and the absorbed conjugated molecules will be exploited. The function of the new 3D self-assembled systems in promoting rationally designed photocatalyzed reactions will also be exploited.