Creation of Novel Functional Supramolecular Organic Chemistry

新型功能超分子有机化学的创造

基本信息

批准号：
15205007
负责人：
IYODA Masahiko
金额：
$ 29.95万
依托单位：
Tokyo Metropolitan University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2005
项目状态：
已结题

项目摘要

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

通过特定分子间相互作用的有机π共轭系统自组装成复杂的，有组织的超分子结构是实现功能性分子材料的有希望的方法。最近已利用许多分子间相互作用，例如氢键，金属配位，CT相互作用和π-π堆积，用于构建所需的超分子结构，例如纤维，丝带，胶带，磁带，纳米管和纳米粒子。最近，尽管S相互作用是溶液中的弱吸引力，但它在晶体中分子的堆积中起着重要作用。这是使用有机导体的坐标S…和π-π堆积相互作用的有机导体的有机导体和超导体（TTF）构建的有机导体的crystal工程技术表明，范德华瓦尔斯和偶极 - 二极二极二极化的相互作用在中性硫原子之间产生了吸引力的吸引力……更多的含量会在水晶中产生更多的效果。氧化态中的相应相互作用基本上也很有利。因此，两个TTF分子倾向于面对面对齐，以在晶体中产生堆叠结构。尽管位置紧密的二聚体TTF/TTF在中性状态下弱稳定，但二聚体TTF/TTF^+在阳离子状态下强烈稳定，以产生混合价形式，因此在固态中的电导率出现。此外，两个阳离子 - 激进物TTF^+/TTF^+在溶液中也具有吸引力的（π-二聚体形成），从而导致在固态中形成莫特的半导体。经常使用有机材料作为分子开关和设备的材料科学家使用。为了设计使用这些应用的π-偏分子，需要详细了解溶液或中间机中自聚集的结构，因为相互关联的π系统的预聚集可能控制分子在固体表面上的排列。考虑到这一点，已经在溶液和固态中构建了氧化还原活性的纳米级结构，并且已经根据TTF低聚物和大环寡聚体的中性和阳离子聚集体的结构作为一个硫酸幼体的π-π-系统研究了。最后，我们成功地构建了导电螺旋供体，具有六角形布置的导电纳米纤维和热色素TTF系统。较少的

项目成果

期刊论文数量（118）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Synthesis of Nonaphenylenes and Dodecaphenylenes Using Electron-Transfer Oxidation of Lipshutz Cuprate Intermediates

Lipshutz 铜酸盐中间体电子转移氧化合成九亚苯基和十二亚苯基

DOI：
发表时间：
2005
期刊：
Chemistry Letters 34
影响因子：
0
作者：
M.Iyoda;M.Wu;Y.Kuwatani;Y.Miyake
通讯作者：
Y.Miyake

T.Enoki, H.Yamazaki, J.Nishijo, A.Miyazaki.K.Ugawa, E.Ogura, Y.Kuwatani, M.Iyoda, Y.V.Sushko: "Novel Magnetism of EDO-TTFX_2 Salts (X=Br,I)"Synth.Met.. 137. 1173-1174 (2003)

T.Enoki、H.Yamazaki、J.Nishijo、A.Miyazaki.K.Ugawa、E.Ogura、Y.Kuwatani、M.Iyoda、Y.V.Sushko：“EDO-TTFX_2 盐 (X=Br,I) 的新颖磁性

DOI：
发表时间：
期刊：
影响因子：
0
作者：
通讯作者：

A twin-rotor system created on a [4]radialene frame

在 [4]radialene 框架上创建的双转子系统

DOI：
发表时间：
2003
期刊：
Org. Lett. 5
影响因子：
0
作者：
Y. Kuwatani;G. Yamamoto;M. Iyoda
通讯作者：
M. Iyoda

Copper-Mediated Simple and Efficient Synthesis of Tribenzohexadehydro[12]annulene and Its Derivatives

铜介导简单高效合成三苯并十六氢[12]轮烯及其衍生物

DOI：
发表时间：
2004
期刊：
Synthesis
影响因子：
0
作者：
M. Iyoda;S. Sirinintasak;Y. Nishiyama A. Vorasingha;F. Sultana;K. Nakao;Y. Kuwatani;H. Matsuyama;M. Yoshida;Y. Miyake
通讯作者：
Y. Miyake

Ferromagnetic Interaction and Metallic Conductivity of Radical Ion Salts (DIEDO)_2 M(mnt)_2 (M =Ni, Pt)

自由基离子盐 (DIEDO)_2 M(mnt)_2 (M =Ni, Pt) 的铁磁相互作用和金属电导率