Creation of Novel Functional Supramolecular Organic Chemistry

通过特定的分子间相互作用将有机π共轭体系自组装成复杂的、有组织的超分子结构，是实现功能分子材料的一种有前途的途径。最近，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，被用来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，我们利用合作的S…开发了一种新的自组装概念S和π-π堆积相互作用。虽然S…S相互作用是溶液中的弱引力，对晶体中分子的堆积起着重要作用。因此，利用合作的S…构建了有机导体和基于四硫富瓦烯的超导体S和π-π的堆积相互作用有机导体的晶体工程认为中性硫原子之间的范德华和偶极-偶极相互作用产生吸引…晶体中的作用力更大。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，以在晶体中产生堆积结构。虽然紧密定位的二聚体TTf/TTf在中性状态下很弱稳定，但二聚体TTf/TTf^+在阳离子状态下却很稳定，形成了混合价形式，从而在固体状态下出现了导电性。此外，两个阳离子自由基TTf^+/TTf^+在溶液中也发生吸引人的相互作用(形成π-二聚体)，从而在固相中形成MoTt绝缘半导体。众所周知，π-共轭分子具有吸电子或大的π-环和盘在溶液中自聚集，而π-共轭分子的表面组织经常被材料科学家利用有机材料作为分子开关和器件。为了设计具有这些用途的π给体分子，需要对溶液或中间相中自聚集体的结构有详细的了解，因为共轭π-体系的预聚集可以控制分子在固体表面的排列。有鉴于此，我们已经实现了在溶液和固体中构建氧化还原活性的纳米结构，并研究了基于TTF齐聚体和大环低聚硫的中性和阳离子聚集体的结构作为一个富硫的π-体系。最后，我们成功地构建了导电螺旋施主、六角排列的导电纳米纤维和热致变色TTF系统。较少

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