Study on the dynamical spin-crossover phenomenon coupled with spinm and charge, and its multifunctionalities

自旋与电荷耦合的动态自旋交叉现象及其多功能性研究

基本信息

批准号：
15350078
负责人：
KOJIMA Norimichi
金额：
$ 9.34万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

项目摘要

In this project, we have synthesized dithiooxalato-bridged iron mixed-valence complexes, (n-C_nH_<2n+1>)_4N[Fe^<II>Fe^<III>(dto)_3] (n=3-6, dto=C_2O_2S_2) and investigated a spin-entropy driven charge transfer phase transition around 120 K, where the electrons of Avogadro's constant transfer cooperatively between the Fe^<II> and Fe^<III> sites, and a ferromagnetic transition at 6.5 K for (n-C_3H_7)_4N[Fe^<II>Fe^<III>(dto)_3]. The charge transfer phase transition takes place for n=3 and 4, while it does not take place between 300 K and 4 K for n=5 and 6. The charge transfer phase transition and the ferromagnetic transition remarkably depend on the hexagonal ring size in the two-dimensional honeycomb network structure of [Fe^<II>Fe^<III>(dto)_3]_∞. The increase of cation size expands the honeycomb ring, which stabilizes the higher temperature phase with Fe^<II> (S=2) and Fe^<III> (S=1/2). Contrary, the contraction of the honeycomb ring stabilizes the lower temperature phase with Fe^<II> (S=0) and Fe^<III> (S=5/2), which was supported by the external pressure effect on the charge transfer phase transition.In order to control the magnetic properties and the electronic state in the dto-bridged iron mixed-valence system by means of photo-irradiation, we have synthesized a photo-sensitive organic-inorganic hybrid system, (SP)[Fe^<II>Fe^<III>(dto)_3] (SP=spiropyran), and investigated the photo-induced effect on the magnetic properties. The UV irradiation changes the structure of spiropyran from the closed form to the open one in (SP)[Fe^<II>Fe^<III>(dto)_3]. The photochromism in spiropyran induces the charge transfer phase transition in the two-dimensional honeycomb network structure of [Fe^<II>Fe^<III>(dto)_3]_∞, and changes the ferromagnetic transition temperature.

在这个项目中，我们合成了二硫代氧化铁的混合价络合物，（N-C_NH_ <2n+1>>）_ 4n [Fe^<ii> fe^<ii> fe^<iii>（dto）_3]（n = 3-6，dto = 3-6，dto = c_2o_2s_2），并调查了一个旋转的循环循环循环循环循环循环驱动器，并绕过循环循环驱动器驱动器驱动器驱动器驱动器驱动器驱动器驱动器驱动器驱动器范围内驱动器驱动器驱动器驱动器驱动器驱动器驱动器驱动器驱动器均可驱动器。在Fe^<ii>和Fe^<iii>位点之间进行常数转移，以及（n-C_3H_7）_4n [Fe^<ii> fe^<iii>（dto）_3]的6.5 k的铁磁过渡。电荷转移相变发生在n = 3和4，而在n = 5和6的300 k和4 k之间进行。电荷转移相变和铁磁过渡明显取决于[fe^fe^fe^<ii> fe^<ii> fe^<ii>（dto）的二维蜂蜜网络中的六边形环大小。阳离子尺寸的增加扩展了蜂窝环，相反，蜂窝环的收缩稳定了较低的温度阶段，通过Fe^<ii>（s = 0）和Fe^<iii>（s = 5/2）稳定下来，这是由外部压力效应在电荷转移中受到外部压力效应的支持。合成了光敏感的有机无机杂交系统，（SP）[Fe^<ii> fe^<iii>（dto）_3]（sp = sp = speropyran），并研究了光诱导的对磁性的影响。紫外线辐照将Spiritpyran的结构从封闭形式变为（SP）[Fe^<ii> fe^<iii>（dto）_3]中的开放形式。 Spiritpyran中的光更色素影响[Fe^<ii> fe^<iii>（dto）_3]_∞的二维蜂窝网络结构中的电荷转移相变，并改变了铁磁过渡温度。

项目成果

期刊论文数量（49）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Crystal Structure and Structural Transition Caused by Charge-transfer Phase Transition for Iron Mixed-valence Complex, (n-C_3H_7)_4N[Fe^<II>Fe^<III>(dto)_3](dto = C_2O_2S_2)

铁混价配合物(n-C_3H_7)_4N[Fe^<II>Fe^<III>(dto)_3](dto = C_2O_2S_2)的晶体结构和电荷转移相变引起的结构转变

DOI：
发表时间：
2004
期刊：
Solid State Commun. 130
影响因子：
0
作者：
M.Itoi;A.Taira;M.Enomoto;N.Matsushita;N.Kojima;Y.Kobayashi;K.Asai;K.Koyama;T.Nakano;Y.Uwatoko;J.Yamaura
通讯作者：
J.Yamaura

小島憲道, 守友浩: "集積型金属錯体の科学-物質機能の多様性を求めて"大川尚士,伊藤翼編,化学同人. 273(113-117) (2003)

小岛纪道、森友浩：“综合金属配合物的科学 - 寻找材料功能的多样性” Naoshi Okawa、Tsubasa Ito (eds.)，Kagaku Doujin 273(113-117) (2003)。