Magnetic Properties of Iron(III) exhibiting Spin-Equilibrium Behavior and Imidazolate-bridged Binuclear Complexes.

表现出自旋平衡行为和咪唑桥双核配合物的铁 (III) 的磁性。

• 批准号: 61470047
• 负责人: AKIRA OHYOSHI
• 金额: $ 3.97万
• 依托单位: Kumamoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1986
• 资助国家: 日本
• 起止时间: 1986 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-61470047/
• 关键词: Spin-equilibrium; Iron(III) complex; Magnetic susceptibility; Imidazolate-bridged complex; Binuclear complex; 磁化率; イミダゾレート架橋銅二核錯体; 反強磁性相互作用; 銅(II)-マンガン(II)-銅(II)三核錯体; 單結晶X線構造解析; 多核銅(II)錯体; ヘリコイド状直鎖構造; イミダゾレート架橋二核金属錯体; 酵素のモデル錯体; 構造パラメーター; 相互

1. Synthesis and Magnetic Properties of Iron(III) Complexes Exhibiting a Spin-Equilibrium Behavior.(1). Five binuclear iron(III) complexes bridged by hyrazine, 1,1'-tetraethylenebis(imidazol), or bis-(pyridine) compounds have been prepared, and their spin-equilibrium behavior between high spin (s=5/2) and low-spin(s=1/2) states has been investigates by means of the temperature dependences of the magnetic susceptibilities and the electronic spectra. The pyridine complex is low-spin, while the bis(imidazole) and the bis(pyridine) complexes showed a spin-equilibrium between high-spin and low-spin states, accompanied by a striking thermochromism in both the solids and solutions.(2). An Iron(III) complex [bis[3-(3-methoxysalicylideneamine)propyl]amino-O,N,N',N",O'](pyridine)-iron(III) Tetraphenylborate with a spinequilibrium has been investigated by means of the temperature dependences of the magnetic susceptibilities, the electronic spectra, and cyclic voltammetry. The pure electronic spec … More tra for high-spin and low-spin species were evaluated from the observed electronic spectra and the equilibrium constants obtained from the magnetic data. The electrontransfer entropy of the Fe<@D13+@>D1 + e Fe<@D2+@>D1 process (deltaS<@D2et@>D2) was obtained as 205 JK<@D1-1@>D1mol<@D1-1@>D1 from the temperature dependence of the cyclic voltammogram.2. synthesis and magnetic properties of imidazolate-bridged binulear complexes.(1). Imidazolate-bridged Cu(II)-Mn(II)- Cu(II) complexes have been prepared and characterized. The magnetic susceptibility data were represented by a spin-only interaction model(1/2-5/2-1/2) with J_<Mn-Cu> value of -13 cm^<-1> for (tfa) complex and -8 cm^<-1> for (hfa) complex.(2). Two imidazolate-bridged binuclear copper(II) complexes[Cu(L)Cu(tfacac)_2]and [Cu(L)Cu(tebima)]-[PF_6][C10_4] ・Me_2CO have been prepared and characterized by elemental analyses, melting points, molar electrical conductivities, i.r., electronic, and e.s.r.spectra, magnetic susceptibilities. The magnetic susceptobolity data gave the antiferromagnetic interaction parameters 2J = 112 cm^<-1> for the former complex and ー140 cm^<-1> for the latter. The e.s.r.spectra of complexes measured in frozen solutions (77K) at X-band frequency showed broad deltaM=1 and weak deltaM=2 absorptions. Less

1.具有自旋平衡行为的铁（III）配合物的合成及磁性研究（一）.本文合成了五种由吡嗪、1，1 ′-四乙烯双咪唑或双吡啶化合物桥联的双核铁（III）配合物，并通过磁性和电子光谱的温度依赖性研究了它们在高自旋（s=5/2）和低自旋（s=1/2）态之间的自旋平衡行为。吡啶配合物是低自旋的，而双（咪唑）和双（吡啶）配合物表现出高自旋和低自旋状态之间的自旋平衡，伴随着显着的热致变色在固体和溶液中。（二）、本文研究了具有自旋平衡的[双[3-（3-甲氧基水杨醛胺）丙基]氨基-O，N，N '，N”，O']（吡啶）-四苯硼酸铁（Ⅲ）配合物的磁性、电子光谱和循环伏安特性。纯电子规格 ...更多信息 从观测到的电子光谱和从磁性数据获得的平衡常数评估高自旋和低自旋物种的TRA。由循环伏安曲线的温度依赖性得到Fe<@D13+@>D1 + e Fe<@D2+@>D1过程的电子转移熵（deltaS<@D2et@>D2）为205 JK<@D1 - 1@> D1 mol <@D1-1@>D1.咪唑桥联双核配合物的合成及磁性研究。（一）.本文合成并表征了咪唑桥联的Cu（II）-Mn（II）- Cu（II）配合物。磁化率数据用纯自旋相互作用模型（1/2-5/2-1/2）表示，（tfa）络合物的J_<Mn-Cu>值为-13 cm ~ <-1>2，<-1>（hfa）络合物的J_值为-8 cm ~ 2。（二）、合成了两种咪唑桥联双核铜配合物[Cu（L）Cu（tfacac）_2]和[Cu（L）Cu（tebima）]-[PF_6][C10_4] ·Me_2CO，并通过元素分析、熔点、摩尔电导率、i.r.电子和E.S.R.光谱，磁磁化率。磁吸光度数据给出了前一种配合物的反铁磁相互作用参数2 J = 112 cm^<-1>，后一种配合物的反铁磁相互作用参数2 J = 140 cm^<-1>。在冷冻溶液（77 K）中测得的X-带频率下的e.s.r.谱显示出宽的δ M =1和弱的δ M =2峰。少

项目成果

Yonezo,Maeda: "Spectroscopic and Magnetic Properties of [Fel_2(salacen)]PF_6(L=Imidazole or N-Methylimidazole); New Examples of Intermediate Electron Relaxation Between S=1/2 and 5/2 States. X-Ray Crystal Structure of [Fe(Him)_2(salacen]PF_6." Journal of

Yonezo,Maeda：“[Fel_2(salacen)]PF_6（L=咪唑或 N-甲基咪唑）的光谱和磁性；S=1/2 和 5/2 态之间中间电子弛豫的新例子。X 射线晶体结构

Y.Maeda: J.Chem.Soc.Dalton Trans.1986. 1115-1123 (1986)

Y.Maeda：J.Chem.Soc.Dalton Trans.1986。

Naohide,Matsumoto: "Synthesis and Characterization of Imidazolate-Bridged Binuclear Copper(II) Complexes." Bulletin of the Chemical Society of Japan. 59. 1609-1610 (1986)

Naohide，Matsumoto：“咪唑酯桥双核铜 (II) 配合物的合成和表征。”

Naohide Matsumoto;Junko KaneSaka;Akira Ohyoshi;Masaaki Nakamura;Susumu Kohata;Hisashi Okawa: Bulletin of the Chemical Society of JAPAN. 60. 3056-3058 (1987)

Naohide Matsumoto;Junko KaneSaka;Akira Ohyoshi;Masaaki Nakamura;Susumu Kohata;Hisashi Okawa：日本化学会通报。

N.Matsumoto;N.Takemoto;A.Ohyoshi;H.Okawa: Bulletin of the Chemical Society of JAPAN. 61. 2987-2986 (1988)

N.Matsumoto；N.Takemoto；A.Ohyoshi；H.Okawa：日本化学会公报。