Development and Functions of Dynamic Supramolecular Systems Coupled with Electronic Systems for Energy Conversion

本计画的主要目的是发展以分子导体与磁铁为基础，并具有动态特性的超分子阳离子的新型分子系统。至于分子导体和磁体的构建块，我们使用[Ni（dmit）2]和其他金属络合物。基于冠醚的亚分子结构与配合物结合形成新的分子体系。本论文主要研究了有机铵和[18]冠-6衍生物在[Ni（dmit）2]盐中的分子旋转体结构，在苯胺基邻位引入-NH 2，合成了（HOPD）+（[18]冠-6）[Ni（dmit）2]晶体。强偶极-偶极相互作用导致阳离子层紧密堆积，阻止了芳环的翻转运动。在苯胺基的间位引入-F和-NH 2，合成了（HMFA）+（dibenzo [18] crown-6）[Ni（dmit）2]和（HMPD）+（dibenzo [18] crown-6）[Ni（dmi 1）2]晶体。HMFA和HMPD盐具有相同的组成和晶体结构。由于HMFA和HMPD具有偶极矩，因此可以通过施加外电场来控制这些分子旋转体的翻转运动。结果表明，该晶体为铁电体，居里温度在350 K左右。在超分子结构中引入金刚烷基铵而不是芳基铵衍生物。在120 K以下，金刚烷基的旋转保持不变，1H-NMR测试证实了这一点。总之，我们在电子活性晶体中引入了超分子旋转体结构，这是实现高效能量转换系统的关键步骤之一。此外，我们可以开发基于分子旋转体结构的新型铁电体。

In this project, we aim at the developments of novel molecular systems based on molecular conductors and magnets with supramolecular cations having dynamic feature. As for the building blocks for molecular conductors and magnets, we are using [Ni (dmit) 2] and other metal complexes. Suplamoleclar structures based on crown ethers are combined with the complexes to form novel molecular systems. In this study, we mainly examined molecular rotator structures of organic ammonium and [18]crown-6 derivatives in [Ni (dmit) 2] salts.We introduced -NH2 at o-position of the anilinium and synthesized (HOPD)+([18]crown-6) [Ni (dmit) 2] crystals. Strong dipole-dipole interaction induced the tight packing of cation layers, which prevented flip-flop motion of aryl rings. On the other hand, [18]crown-6 was rotating in the crystal as in the case of (PhNH3) ([18] crown-6) (Ni (dmit) 2).We introduced -F and -NH2 at m-position of the anilinium and synthesized (HMFA)+(dibenzo[18]crown-6) [Ni (dmit) 2] and (HMPD)+(dibenzo [18] crown-6) [Ni (dmi1) 2] crystals. HMFA and HMPD salts gave the same composition and crystal structures.Since HMFA and HMPD have dipole moments, it was possible to control the flip-flop motion of these molecular rotators by applying external electric field. It was proved that the crystal was the ferroelectrics with the Curie temperature of at around 350 K. Adamantylammonium was introduced in the supuramolecular structure instead of arylammonium derivatives. In the crystals, the rotation of adamantly group was maintained below 120 K, which was confirmed by 1H-NMR measurements.In conclusion, we introduced supramolecular rotator structures in electronic active crystals, which is one of the key steps to realize highly efficient energy conversion systems. In addition, we could develop novel ferroelectrics based on molecular rotator structures.