Artificial bioinorganic clusters of dinuclear 3d-transition metal ions coordinated by an inorganic coordination ligand
Artificial bioinorganic clusters of dinuclear 3d-transition metal ions coordinated by an inorganic coordination ligand
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由无机配位体配位的双核 3d 过渡金属离子的人工生物无机簇
DOI：
10.1016/j.jinorgbio.2019.110821
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发表时间：
2019
影响因子：
3.9
通讯作者：
Hayashi Yoshihito
中科院分区：
文献类型：
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作者：
Sugiarto;Kawamoto Keisuke;Hayashi Yoshihito
开发了一种新的生物相关的立方烷型人工无机配体，以支持Mn（II）、Co（II）、Ni（II）、Zn（II）、Fe（III）和In（III）的3d过渡金属离子。所有反应均生成双核阳离子簇[（{Co（tacn）} 2 HMo 3 O 13·H2O）{M（H2O）2}]2n+（M = Mn ~（2+）（4 Mn），Co ~（2+）（4Co），Ni ~（2+）（4 Ni），Zn ~（2+）（4 Zn），n = 2; M = Fe ~（3+）（5），In ~（3+）（6），n = 4），其中tacn为1，4，7-三氮杂环壬烷配体的缩写。簇4根本不溶于任何溶剂以防止重结晶或进一步表征，而簇5和6的高溶解度允许我们表征溶液状态性质。双核核以固定距离分开，对于M（II）络合物为5.66-5.77 μ m，对于M（III）络合物为5.45-5.65 μ m。每个3d-过渡金属离子由CoMo_3 O_3（OH）基团形成的立方烷单元中的两对顺式氧化基团支撑，并且3d-过渡金属中心上的剩余两个位置被两个水分子占据。立方烷单元上的羟基基团通过双核中心之间的分叉氢键提供了相互作用途径。在-0.73、-0.91和-1.16 mVvsFc+/Fc处观察到5 in循环伏安法的三个连续阶梯还原波，与氧化还原非活性In 3+络合物的比较表明，两个铁中心通过无机配体相互作用，在-0.91 mVvsFc+/Fc处观察到还原波。
A new biologically relevant cubane-type artificial inorganic ligand was developed to support 3d-transition metal ions of Mn(II), Co(II), Ni(II), Zn(II), Fe(III), and also In(III). All of the reactions produce dinuclear cationic clusters of [({Co(tacn)}2HMo3O13∙H2O){M(H2O)2}]2n+(M = Mn2+(4Mn), Co2+(4Co), Ni2+(4Ni), Zn2+(4Zn), n = 2; M = Fe3+(5), In3+(6), n = 4), where tacn is the abbreviation of 1,4,7-triazacyclononane ligand. Clusters4do not dissolve in any solvents at all to prevent the recrystallization or the further characterization whereas the high solubility of clusters5and6allowed us to characterize the solution state properties. The dinuclear cores are separated at a fixed-distance in the range of 5.66–5.77 Å for M(II) complexes and 5.45–5.65 Å for M(III) complexes. Each 3d-transition metal ion is supported by two pairs ofcis-oxido groups from a cubane unit formed by CoMo3O3(OH) group, and remaining two sites on the 3d-transition metal centers are occupied by two water molecules. The hydroxido group on the cubane unit provides an interaction route through bifurcated hydrogen bondings between dinuclear centers. Three consecutive stepwise reduction waves were observed at −0.73, −0.91, and −1.16 mVvsFc+/Fc for5in cyclic voltammetry and the comparison with the redox inactive In3+complex revealed that two iron centers are interacted each other through the inorganic ligand which gave a reduction wave observed at −0.91 mvvsFc+/Fc.