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

动态超分子系统与能量转换电子系统耦合的发展和功能

• 批准号: 16074201
• 负责人: NAKAMURA Takayoshi
• 金额: $ 10.37万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16074201/
• 关键词: Metal complexes; Molecular Rotators; Ferroelectrics; Supramolecules; Crystal structure; Molecular magnetism; Molecular conductors; クラウンエーテル; イオン電動; イオン電導; イオン伝導

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.

在本项目中，我们致力于开发基于具有动力学特性的超分子阳离子的分子导体和磁体的新型分子体系。至于分子导体和磁体的构建块，我们使用的是[Ni(Dmit)2]和其他金属络合物。基于冠醚的超分子结构与配合物结合形成了新的分子体系。在本研究中，我们主要研究了有机铵和[18]冠-6衍生物在[Ni(Dmit)2]盐中的旋光结构，在苯胺环的o-位引入-NH2，合成了(HOPD)+([18]冠-6)[Ni(Dmit)2]晶体。强烈的偶极-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。另一方面，与(PhNH3)([18]冠-6)(Ni(Dmit)2)一样，[18]冠-6在晶体中是旋转的。我们在苯胺的m位引入-F和-NH2，合成了(HMFA)+(二苯并[18]冠-6)[Ni(Dmit)2]和(HMPD)+(二苯并[18]冠-6)[Ni(Dmi1)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，因此有可能通过外加电场来控制这些分子旋转体的触发运动。结果表明，该晶体是居里温度在350K左右的铁电体，在超分子结构中引入了金刚烷基铵，而不是芳基铵的衍生物。经1H-核磁共振测试证实，晶体中固定性基团的旋转度保持在120K以下。最后，我们在电子活性晶体中引入超分子旋转体结构，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材料。

项目成果

Molecular-assembly nanostructures of 1 : 1 mixed Langmuir-Blodgett films of amphiphihc bis-TTF macrocycle and F4-TCNQ

两亲双-TTF大环和F4-TCNQ 1:1混合Langmuir-Blodgett薄膜的分子组装纳米结构

• 发表时间: 2006
• 期刊: Colloids and Surfaces A 284
• 作者: Y.Tatewaki;T.Akutagawa;T.Nakamura;H.Hasegawa;S.Mashiko;C.Christensen;J.Becher
• 通讯作者: J.Becher

Molecular Rotators in[Ni(dmit)_2]Single Crystals

[Ni(dmit)_2]单晶中的分子旋转体

• 发表时间: 2008
• 作者: Harutoki Shimura;Masafumi Yoshio;Koji Hoshino;Tomohiro Mukai;Hiroyuki Ohno;Takashi Kato;Yuuta Fujikawa;T. Nakamura and T. Akutagawa
• 通讯作者: T. Nakamura and T. Akutagawa

Molecular Rotators in Magnetic and Conducting Crystals; Structures and Electronic Properties

磁性和导电晶体中的分子旋转体；

• 发表时间: 2007
• 作者: Yasumichi Matsumoto;Shintaro Ida;Taishi Inoue;T. Nakamura
• 通讯作者: T. Nakamura

Large anisotropy and effect of deuteration on permittivity in an olefin copper(I) complex.

• DOI: 10.1002/anie.200700629
• 发表时间: 2007-09
• 期刊: Angewandte Chemie
• 作者: Qiong Ye;Hong Zhao;Zhirong Qu;D. Fu;R. Xiong;Yi Cui;T. Akutagawa;P. Chan;Takayoshi Nakamura

Structural Change in Langmuir-Blodgett Films of Bis-tetrathiafulvalene Annelated Macrocycle Tetrafuluorotetracyanoquinodimethane Charge Transfer Complex

双四硫富瓦烯退火大环四氟四氰基醌二甲烷电荷转移配合物Langmuir-Blodgett薄膜的结构变化

• 发表时间: 2004
• 期刊: Mol.Cryst.Liq.Cryst. 424
• 作者: Y.Tatewaki;et al.
• 通讯作者: et al.