Akutagawa Tomoyuki, Nakamura Takayoshi
Research Institute for Electronic Science, Hokkaido University, N20W10 kita-ku, Sapporo, 001-0020, Japan.
Dalton Trans. 2008 Dec 7(45):6335-45. doi: 10.1039/b808748b. Epub 2008 Oct 9.
Artificial molecular rotators were designed in an attempt to achieve unidirectional molecular rotation. Supramolecular assemblies of cations and crown ethers in the solid state were shown to form rotator structures, diverse in their rotational symmetry and frequency. The counter cation of [Ni(dmit)2]- anion, bearing one S=1/2 spin, was used to couple molecular rotation to magnetic properties. Random rotation of [18]crown-6 molecules was first observed in the Cs(+)2([18]crown-6)(3) supramolecule, where the rotational freedom of [18]crown-6 rotators was evidently coupled to the magnetic properties of [Ni(dmit)2]-pi-dimer. In other cases, dual rotary motions of anilinium([18]crown-6) and rotator-stator assemblies of (adamantylammonium)(dibenzo[18]crown-6) were investigated as a means to control rotational symmetries and frequencies in the solid state. The supramolecular approach for construction of molecular rotator-stator assemblies in the solid state is a convenient approach to the design of molecular rotary functionality in [Ni(dmit)2]- salts.
人们设计了人工分子转子，试图实现分子的单向旋转。研究表明，阳离子与冠醚在固态下形成的超分子组装体可构成转子结构，其旋转对称性和频率各不相同。带有一个S = 1/2自旋的[Ni(dmit)2]-阴离子的抗衡阳离子被用于将分子旋转与磁性质相耦合。首次在Cs(+)2([18]冠-6)(3)超分子中观察到[18]冠-6分子的随机旋转，其中[18]冠-6转子的旋转自由度明显与[Ni(dmit)2]-π二聚体的磁性质相耦合。在其他情况下，研究了苯胺鎓([18]冠-6)的双旋转运动以及(金刚烷基铵)(二苯并[18]冠-6)的转子-定子组装体，以此作为控制固态下旋转对称性和频率的一种手段。在固态下构建分子转子-定子组装体的超分子方法是设计[Ni(dmit)2]-盐中分子旋转功能的便捷方法。
