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中，具有光磁性等多种功能，在器件方面的应用受到广泛关注。本项目的主要研究内容是利用插层分子的光致异构作用在室温下研究光致自旋交叉现象，以及光致变色分子耦合的二维铁磁体系的磁性转变。(1)铁的混合价配合物（n-C_3 H_7）_4N[Fe^<II>Fe^<III>（dto）_3]（dto = C_2O_2S_2）在120 K附近发生了与自旋和电荷耦合的电荷转移相变，在6.5 K发生了铁磁相变。这些相变显着依赖于阳离子的大小。为了利用光辐射调控该体系的磁性，我们合成了（SP）[Fe^<II>Fe^<III>（dto）_3]（SP =螺吡喃），并发现该体系的磁性随光辐射强度的增加而增加，但由于光辐射强度的增加，其磁性随光辐射强度的增加而增加。 关于我们 紫外光照射使螺吡喃的结构由封闭型转变为开放型。该体系中螺吡喃的光致变色性控制了铁磁转变温度和矫顽场以及电荷转移相变。此外，我们还发现（SP）[Fe^ Fe^（dto）_3]中螺吡喃的光致变色性诱导<II><III>了[Fe^<II>Fe^<III>（dto）_3]_∞的电荷转移相变。(2)我们合成了几种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耦合的情况下，我们发现，二芳基乙烯的异构化控制磁有序温度。在氢氧化钴基二维铁磁体（Co-LDHs）中，阴离子二芳基乙烯在固态下发生可逆光异构化反应，光异构化反应由开放式向封闭式转变，导致Curie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