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

光致变色分子嵌入到磁性体系中提供了令人着迷的光磁性等多功能，其在器件上的应用备受关注。本项目的主要课题是利用插层分子的光异构化发展室温下的光诱导自旋交叉现象，以及发展与光致变色分子耦合的二维铁磁体系的磁性转变。题目题目的结果如下：(1)铁杂价配合物（n-C_3H_7）_4N[Fe^<II>Fe^<III>(dto)_3] （dto = C_2O_2S_2）在120k左右表现出自旋和电荷耦合的电荷转移相变，在6.5 K时表现出铁磁跃迁。这些相变显著地依赖于阳离子的大小。为了用光照射控制该体系的磁性能，我们合成了（SP） [Fe^<II>Fe^<III>(dto)_3] （SP =螺吡喃），并发现…More紫外照射使螺吡喃在固体状态下由封闭结构变为开放结构。该体系中螺吡喃的光致变色性控制着铁磁转变温度和矫顽力场以及电荷转移相变。此外，我们还发现螺吡喃在（SP） [Fe^<II>Fe^<III>(dto)_3]中的光致变色诱导了[Fe^<II>Fe^<III>(dto)_3]_∞中的电荷转移相变。(2)合成了几种由二维铁磁体和光致变色二芳烯组成的有机-无机杂化体系。在层状钙钛矿型卤化铜与阳离子二乙基乙烯偶联的情况下，我们发现二乙基乙烯的异构化控制了磁有序温度。在羟基钴基二维铁磁体（Co-LDHs）中，我们发现阴离子二乙烯在固态下发生可逆的光异构化，并且从开放形态到封闭形态的光异构化诱导居里温度从9 K提高到20 K。少

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