Constructions of external stimuli-induced electron transfer systems

外部刺激诱导的电子转移系统的构建

• 批准号: 20750041
• 负责人: NIHEI Masayuki
• 金额: $ 2.83万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Young Scientists (B)
• 财政年份: 2008
• 资助国家: 日本
• 起止时间: 2008 至 2009
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-20750041/
• 关键词: 電子移動; 外場応答; 多重安定性; 物性変換

Mixed-valence heterometal complexes are good candidates for a system exhibiting entropy-driven electron transfer, because the electron transfer associates relatively large structural changes. In this study, tetranuclear molecular squares with various substituent groups, [Fe^<III>_2Co^<II>_2(CN)_6(L1)_2(L2)_4] (L1 and L2 are multi-dentate ligands), were prepared. The molecular squares exhibited spin transition between HS ([Fe^<III>_<LS>(S=1/2)Co^<II>_<HS>(S=3/2)]) and LS ([Fe^<II>_<LS> (S=0)Co^<III>_<LS>(S=0)]) states induced by thermal intramolecular electron transfer. The intramolecular electron transfer can be controlled by chemical modification, where electron donating groups on the ligands modified the redox potentials of metal ions, leading to fine tuning of spin transition temperatures. In addition, protonation to terminal nitrogen atoms of cyanide lead to a novel protonation-induced spin transition between LS and HS states.

混合价异金属配合物是表现出熵驱动的电子转移的系统的良好候选者，因为电子转移关联相对大的结构变化。本研究合成了具有不同取代基的四核分子方[Fe^<III>_2Co^<II>_2（CN）_6（L1）_2（L2）_4]（L1和L2为多齿配体）。在热分子内电子转移的作用下，分子正方形出现了HS（[Fe^<III>_<LS>（S=1/2）Co^<II>_<HS>（S=3/2）]）和LS（[Fe^<II>_<LS>（S=0）Co^<III>_<LS>（S=0）]）之间的自旋跃迁。分子内的电子转移可以通过化学修饰来控制，其中配体上的供电子基团修饰了金属离子的氧化还原电位，导致自旋转变温度的微调。此外，质子化的末端氮原子的氰化物导致一个新的质子化诱导的自旋跃迁之间的LS和HS状态。

项目成果

Syntheses, structures and magnetic properties of iron(II) complexes with bulky tridentate ligands

具有大体积三齿配体的铁(II)配合物的合成、结构和磁性

• 发表时间: 2008
• 期刊: Inorg. Chim. Acta. 361
• 作者: M. Nihei;et.al.
• 通讯作者: et.al.

Peculiarity in the electronic structure of Cu(II) complex ferromagnetically coupled with bisimino nitroxides

• DOI: 10.1021/jp802810s
• 发表时间: 2008-09-18
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY A
• 影响因子: 2.9
• 作者: Ikoma, Tadaaki;Oshio, Hiroki;Nihei, Masayuki
• 通讯作者: Nihei, Masayuki

Cyanide-bridged tri- and tetra-nuclear spin crossover complexes

• DOI: 10.1016/j.poly.2008.10.051
• 发表时间: 2009-06
• 期刊: Polyhedron
• 影响因子: 2.6
• 作者: M. Nihei;M. Ui;H. Oshio

The light-induced spin transition of tetranuclear spin crossover complex [Fe4(CN)4(bpy)4(tpa)2](PF6)4

• DOI: 10.1088/1742-6596/148/1/012033
• 发表时间: 2009-02
• 作者: Taishi Nishihara;M. Nihei;H. Oshio;Koichiro Tanaka

Cyanide-bridged iron(II,III) cube with multistepped redox behavior

• DOI: 10.1021/ic7024582
• 发表时间: 2008-07-21
• 期刊: INORGANIC CHEMISTRY
• 影响因子: 4.6
• 作者: Nihei, Masayuki;Ui, Mayumi;Oshio, Hiroki
• 通讯作者: Oshio, Hiroki