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

在这个项目中，我们的目标是基于具有动态特征的超分子阳离子的分子导体和磁体的新型分子体系的发展。至于分子导体和磁铁的构建块，我们正在使用[Ni (dmit) 2]和其他金属配合物。基于冠醚的超分子结构与配合物结合形成新的分子体系。在本研究中，我们主要研究了[Ni (dmit) 2]盐中有机铵和[18]冠-6衍生物的分子旋转器结构。我们在苯胺的o位引入-NH2，合成了(HOPD)+([18]冠-6)[Ni (dmit) 2]晶体。强的偶极-偶极相互作用导致阳离子层紧密堆积，阻止了芳基环的翻转运动。与（PhNH3） （[18] crown-6） （Ni (dmit) 2）一样，[18]crown-6在晶体中旋转。我们在苯胺的m位引入-F和-NH2，合成了(HMFA)+（二苯并[18]冠-6）[Ni (dmi1) 2]和(HMPD)+（二苯并[18]冠-6）[Ni (dmi1) 2]晶体。HMFA和HMPD盐的组成和晶体结构相同。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器的翻转运动。结果表明，该晶体为铁电体，居里温度约为350 K。在超分子结构中引入金刚胺代替芳胺衍生物。在晶体中，固结基团的旋转在120 K以下保持不变，这一点通过1H-NMR测量得到了证实。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，我们还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.