Creation of Novel Functional Supramolecular Organic Chemistry

有机π-共轭体系通过分子间的相互作用自组装成复杂的、有序的超分子结构是实现功能分子材料的一种很有前途的方法。近年来，许多分子间相互作用如氢键、金属配位、CT相互作用和π-π堆积已被用于构建所需的超分子结构，如纤维、带、带、纳米管和纳米颗粒。最近，我们发展了一个新的概念，自组装通过使用合作的S. S和π-π堆积相互作用。虽然S. S相互作用在溶液中是一种弱吸引力，但它对晶体中分子的堆积起着重要作用。因此，基于四硫富瓦烯（TTF）的有机导体和超导体是利用S. S和π-π堆积相互作用构建的。有机导体的晶体工程表明，中性硫原子之间的货车德瓦耳斯和偶极-偶极相互作用引起吸引。 关于我们 在晶体中施加力。氧化态的相应相互作用在能量上也是有利的。因此，两个TTF分子倾向于面对面排列，以在晶体中产生堆叠结构。虽然紧密定位的二聚TTF/TTF在中性状态下稳定性弱，但二聚TTF/TTF^+在阳离子状态下稳定性强，产生混合价态，因此在固态下出现导电性。此外，两个阳离子自由基TTF^+/TTF^+之间也存在吸引作用已知具有吸电子或大π环和圆盘的π共轭分子在溶液中自聚集，而π共轭分子的表面组织经常被采用有机材料作为分子开关和器件的材料科学家使用。为了设计具有这些应用的π-供体分子，需要对溶液或中间相中的自聚集体的结构的详细知识，因为共轭π-系统的预聚集可以控制分子在固体表面上的排列。考虑到这一点，已经实现了溶液和固态中的氧化还原活性纳米级结构的构建，并且已经研究了基于TTF低聚物和大环低聚噻吩的中性和阳离子聚集体的结构作为富硫π-系统。最后，我们成功地构建了导电螺旋给体、具有六方排列的导电纳米纤维和热致变色TTF系统。少

Self-assembly of organic π-conjugated systems into complex, organized supramolecular structures via specific intermolecular interactions is a promising way to realize functional molecular materials. Many intermolecular interactions such as hydrogen bonding, metal coordination, CT interaction, and π-π stacking have been utilized recently to construct desired supramolecular architectures such as fibers, ribbons, tapes, nanotubes, and nanoparticles. Recently, we have developed a new concept of self-assembly by the use of cooperative S…S and π-π stacking interactions. Although S…S interaction is a weak attractive force in solution, it plays an important role in packing of molecules in crystals. Thus, organic conductors and superconductors based on tetrathiafulvalenes (TTF) are constructed using cooperative S…S and π-π stacking interactionsCrystal engineering of organic conductors suggests that van der Waals and dipole-dipole interactions between neutral sulfur atoms give rise to an attract … More ive force in crystals. The corresponding interactions in the oxidation state are also energetically favorable. Therefore, two TTF molecules tend to align face-to-face to produce a stacking structure in crystals. Although the closely located dimeric TTF/TTF is weakly stable in the neutral, state, the dimeric TTF/TTF^+ is strongly stabilized in the cationic state to produce a mixed valence form and hence the appearance of conductivity in the solid state. Moreover, two cation-radicals TTF^+/TTF^+ also interact attractively (π-dimer formation) in solution leading to the formation of a Mott-insulating semi-conductor in the solid state.It is known that π-conjugated molecules with either electron-withdrawing or large π-circles and disks self-aggregate in solution, while the surface organization of π-conjugated molecules is frequently used by material scientists employing organic materials as molecular switches and devices. To design a π-donor molecules with these applications, detailed knowledge of the structures of self-aggregates in solution or in mesophase is required, because pre-aggregation of conjugated π-systems may control the arrangement of the molecules on the solid surface. With this in mind, construction of a redox-active nanoscale architecture in solution and in the solid state has been achieved, and structures of neutral and cationic aggregates based on TTF oligomers and macrocyclic oligothiophenes have been investigated as a sulfur-rich π-system. Finally, we suceeded to construct conductive helical donors, conductive nanofibers having hexagonal arrangement, and thermochromic TTF systems. Less