Progress of Conjugated Phenomena Coupled with Spin and Photon for Assembled Hetero-Molecular System by Using Coordination Space

将光致变色分子嵌入磁性体系具有光磁性等多种功能，使其在器件中的应用备受关注。本课题的主要内容是利用插层分子的光致异构化发展室温下的光致自旋交叉现象，以及发展与光致变色分子耦合的二维铁磁性体系的磁性转变。(1)铁的混价络合物(n-C_3H_7)_4N[Fe^&lt；II&gt；Fe^&lt；III&gt；(dto)_3](dTO=C_2O_2S_2)在120K附近发生与自旋和电荷耦合的电荷转移相变，在6.5K发生铁磁相变。这些相变明显依赖于阳离子的大小。为了通过光辐射控制该体系的磁性，我们合成了(SP)[Fe^&lt；II&gt；Fe^&lt；III&gt；(Dto)_3](SP=螺吡喃)，发现…紫外光照射使螺吡喃的固态结构由封闭状态转变为开放状态。该体系中螺吡喃的光致变色控制着铁磁相变温度和矫顽场以及电荷转移相变。此外，我们还发现螺吡喃在(SP)[Fe^&lt；II&gt；Fe^&lt；III&gt；(Dto)_3]中的光致变色导致了[Fe^&lt；II&gt；Fe^&lt；III&gt；(Dto)_3]_∞的电荷转移相变。(2)合成了由二维铁磁体和光致变色二芳基乙烯组成的有机-无机杂化体系。在层状钙钛矿型卤化铜与阳离子二芳基乙烯偶联的情况下，我们发现二芳基乙烯的异构化控制了磁性有序温度。以氢氧化钴为基础的二维铁磁体(Co-LDHs)为例，我们发现阴离子二芳基乙烯在固态下发生可逆光异构化，从开式到封闭式的光异构化导致居里温度从9K提高到20K。

Intercalation of photochromic molecule into magnetic system provides fascinating multi-functionalities such as photo-magnetism, which gains much attention for their application to devices. The main subjects in this project were the development of photo-induced spin-crossover phenomena at room temperature by using the photo-isomerization of intercalated molecule, and the development of the transformation of magnetism for two-dimensional ferromagnetic system coupled with photochromic molecule.The outcomes of the title subject are as follows. (1) Iron mixed-valence complex, (n-C_3H_7)_4N[Fe^<II>Fe^<III>(dto)_3] (dto = C_2O_2S_2), shows the charge transfer phase transition coupled with spin and charge around 120 K and a ferromagnetic transition at 6.5 K. These phase transitions remarkably depend on the cation size. In order to control the magnetic properties in this system by means of photo-irradiation, we have synthesized (SP) [Fe^<II>Fe^<III>(dto)_3] (SP = spiropyran), and found that the … More UV irradiation changes the structure of spiropyran from the closed form to the open one in solid state. The photochromism of spiropyran in this system controls the ferromagnetic transition temperature and the coercive field as well as the charge transfer phase transition. Moreover, we have found that the photochromism of spiropyran in (SP) [Fe^<II>Fe^<III>(dto)_3] induces the charge transfer phase transition in [Fe^<II>Fe^<III>(dto)_3]_∞. (2) We have synthesized several organic-inorganic hybrid systems consisting of two-dimensional ferromagnets and photochromic diarylethenes. In the case of layered perovskite-type copper halides coupled with cationic diarylethene, we found that the isomerization of diarylethene controls the magnetic ordering temperature. In the case of cobalt hydroxide-based 2D ferromagnet (Co-LDHs), we found that the reversible photo-isomerization of anionic diarylethene takes place in solid state and the photo-isomerization from the open form to the close form induces the enhancement of Curie temperature from 9 K to 20 K. Less