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Studies on Magneto-Photo Multifunctional System of Polynuclear Complexes Comprised by Discrete Metal Complexes

离散金属配合物多核配合物磁光多功能体系的研究

基本信息

批准号：
15510092
负责人：
KOIKAWA Masayuki
金额：
$ 2.43万
依托单位：
SAGA University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
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

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15510092/
关键词：
Trinuclear Complex Manganese Complex Copper Complex Vanadium Complex Nano-size Complex X-ray Crystallography Redox Property Dye solar cell

项目摘要

The new polydentate ligands, H_4L4-X and H_3L5-X(X=H,CH_3,Br), combined two separative coordination sites have been synthesized by reaction of salicylaldehyde homologues and 4,6-diamino-resorcinol. The new trinuclear manganese(III) complexes, [Mn(L5-X)(CH_3OH)]_3 (X=-H;1,-CH_3;2,and -Br;3) have been prepared and characterized by X-ray structure analysis. The trinuclear structure of 1 is shown in Figure 1.Three manganese(III) centers are separated by (L5-H)^<3->, and the Mn...Mn distances lie in the range 8.07(3)-8.18(1) Å. Each manganese ion adopts an elongated octahedral configuration along with O_<solvent>-Mn-N_<oxazoline> axis. The CPK models for 1 are shown in Figure 2.The molecular structure is regarded as a large trigonal pyramid with cavity. Extent of the cavity is estimated as 3 Å in diameter, and the complexes potentially can incorporate small molecules into the cavity. It is expected that the cavity is well adjustable for NH_4^+ because it has hydrophilic oxygens and C_3 symmetry. The reaction of complex 1 and NH_4PF_6 in chloroform gave reddish brown microcrystals. The IR spectrum of the obtained compound showed strong N-H and P-F vibrations at 3212 and 847 cm^<-1>, respectively. Molar conductivity of the products determined in DMF was 96 Scm^2mor^<-1>. The results suggest that the obtained compound formulated as [Mn_3(L5-H)_3(CH_3OH)_3(NH_4)]_3PF_6 (1'). The ammonium ion in 1' was incorporated into the cavity of trinuclear complex unit.

通过水杨醛同系物与4，6-二氨基间苯二酚反应，合成了新的多齿配体H_4L_4-X和H_3L_5-X(X=H，CH_3，Br)。合成了新的三核锰(III)配合物[Mn(L5-X)(CH3OH)]3(X=-H；1，-CH3；2和-Br3；3)，并对其进行了X射线结构分析。化合物1的三核结构如图1所示，三个锰(III)中心由(L5-H)^-lt；3-&gt；隔开，其间距为8.07(3)-8.18(1)Å。每个锰离子都采用拉长的八面体构型，并带有O_&lt；溶剂&gt；-Mn-N_&lt；恶唑啉&gt；轴。1的CPK模型如图2所示。分子结构被认为是一个大的带有空腔的三角金字塔。空腔的范围被估计为直径为3Å，并且这些复合体可能会将小分子结合到空腔中。由于腔体具有亲水性和C_3对称性，可以很好地调节NH_4~(2+)。络合物1与NH_4PF_6在氯仿中反应生成红棕色微晶。红外光谱显示化合物在3212和847 cm^&lt；-1&gt；处有较强的N-H和P-F振动。在DMF中测得产物的摩尔电导率为96scm~(-2)。结果表明，所得化合物的分子式为[Mn3(L5-H)3(CH3OH)3(NH4)]3PF6(1‘)。1‘中的氨离子被引入到三核络合物单元的空腔中。