Formation and Functions of Self-Assembled Molecular Systems of Supramolecular Ions and Inherent Electrons

我们在[Ni(Dmit)2]晶体中引入了由无机阳离子和冠醚组成的超分子阳离子，开发了电子连接和离子导电共存的新型分子体系，并利用超分子阳离子结构调节了晶体中的[Ni(Dmit)2]^-组装，揭示了通过分子组装控制可以控制磁性和电子学性质。为了从分子电荷转移络合物开发纳米材料和器件，我们研究了电荷转移络合物分子膜的形成。特别是，我们利用朗缪尔-布洛吉特方法成功地制备了单组分导电膜。此外，我们还研究了TTF骨架直接附着于金表面的自组装单分子膜。我们发现，当我们将Langmuir-Blodgett方法应用于具有离子识别能力的大环TTF分子时，分子形成了纳米线结构。此外，当我们使用云母衬底时，纳米线识别表面的离子阵列并定向特定的方向。这些结果有力地表明，分子电荷转移络合物对于发展未来的分子电子器件是非常有用的。

We introduced supramolecular cations composed of inorganic cations and crown ethers into [Ni(dmit)2 crystals and developed novel molecular systems in which electronic condction and ionic conduction coexisted.We also regulated [Ni(dmit)_2]^- assemblies in the crystal utilizing supramolecular cation structures and revealed that we could control magnetic and electronic properties through the molecular-assembly control.To develop nanometer-size materials and devices from molecular charge transfer complexes, we investigated the formation of molecular films of charge transfer complexes. Especially, we used Langmuir-Blodgett method and succeeded in forming single-component conducting films. In addition, we studied self-assembly monolayers in which TTF skeleton directly attached to gold surface. We found that when we apply the Langmuir-Blodgett method to macrocyclic TTF molecule that has ion-recognition ability, the molecules forms nanowire structures. Moreover, when we used mica substrates, the nanowires recognized ionic array of the surface and oriented specific directions. These results strongly indicate that the molecular charge transfer complexes are quite useful to developing future molecular electronic devices.