Strategies for the assembly of homo- and hetero-nuclear metallosupramolecules containing 2,2′ : 6′,2″-terpyridine metal-binding domains
Strategies for the assembly of homo- and hetero-nuclear metallosupramolecules containing 2,2′ : 6′,2″-terpyridine metal-binding domains
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含有 2,2 : 6,2"-三联吡啶金属结合结构域的同核和异核金属超分子的组装策略
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发表时间：
1995
期刊：
影响因子：
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通讯作者：
A. C. Thompson
中科院分区：
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作者：
E. Constable;A. C. Thompson
阐述了聚合合成金属超分子低聚物的新策略。[Ru（X-terpy）Cl_3]与6′，6 ″-二（2-吡啶基）-2，2 ′：4′，4 ″：2″，2 ′-吡啶季铵盐（dpqtpy）在乙二醇中反应生成配体配合物[Ru（X-terpy）（dpqtpy）][PF_6]_2（X-terpy = terpy，eoterpy，cterpy或msterpy）。这些配合物具有一个非配位的三联吡啶（terpy）结构域，并与铁（II）盐瞬间反应得到异三核配合物[（X-terpy）Ru（dpqtpy）Fe（dpqtpy）Ru（X-terpy）][PF 6]6。与乙酸钴（II）的类似反应得到顺磁性d 7钴（II）配合物[（X-terpy）Ru（dpqtpy）Co（dpqtpy）Ru（X-terpy）][PF 6]6，其可以被氧化成动力学惰性的反磁性d 6钴（III）配合物[（X-terpy）Ru（dpqtpy）Co（dpqtpy）Ru（X-terpy）][PF 6]7。[Ru（X-terpy）（dpqtpy）][PF 6]2与“RuCl 3·nH 2 O”反应产生同三核配合物[（terpy）Ru（dpqtpy）Ru（dpqtpy）Ru（dpqtpy）Ru（terpy）][PF 6]6。通过[Ru（terpy）（dpqtpy）][PF_6]_2与[Os（terpy）Cl_3]反应，合成了锇-钌异双核配合物[（terpy）Ru（dpqtpy）Os（terpy）][PF_6]_4。通过[Ru（X-terpy）（dpqtpy）][PF 6]2与等摩尔量的[Ru（Y-terpy）Cl 3]反应，合成了一些具有代表性的混合配体同双核配合物[（X-terpy）Ru（dpqtpy）Ru（Y-terpy）][PF 6]4。具有混合终止剂配体的具体实例是[（terpy）Ru（dpqtpy）Ru（dmterpy）][PF 6]4、[（terpy）Ru（dpqtpy）Ru（msterpy）][PF 6]4和[（dmterpy）Ru（dpqtpy）Ru（msterpy）][PF 6]4。所有的化合物进行了充分的表征，并详细的光谱，光谱和电化学研究进行了描述。
A new strategy for the convergent synthesis of metallosupramolecular oligomers has been elaborated. The key step is the formation of the ligand-complexes[Ru(X-terpy)(dpqtpy)][PF6]2(X-terpy = terpy, eoterpy, cterpy or msterpy) from the reaction of [Ru(X-terpy)Cl3] with 6′,6″-di(2-pyridyl)-2,2′ :4′,4″ :2″,2‴-quaterpyridine (dpqtpy) in ethane-1,2-diol. These complexes have one non-co-ordinated terpyridine (terpy) domain, and reacted instantaneously with iron(II) salts to give the heterotrinuclear complexes [(X-terpy)Ru(dpqtpy)Fe(dpqtpy)Ru(X-terpy)][PF6]6. Similar reactions with cobalt(II) acetate gave the paramagnetic d7 cobalt(II) complexes [(X-terpy)Ru(dpqtpy)Co(dpqtpy)Ru(X-terpy)][PF6]6 which may be oxidised to the kinetically inert diamagnetic d6 cobalt(III) complexes [(X-terpy)Ru(dpqtpy)Co(dpqtpy)Ru(X-terpy)][PF6]7. The reaction of [Ru(X-terpy)(dpqtpy)][PF6]2 with ‘RuCl3·nH2O’ yielded the homotrinuclear complex [(terpy)Ru(dpqtpy)Ru(dpqtpy)Ru(terpy)][PF6]6. The ruthenium–osmium heterodinuclear complex [(terpy)Ru(dpqtpy)Os(terpy)][PF6]4 was readily obtained from the reaction of [Ru(terpy)(dpqtpy)][PF6]2 with [Os(terpy)Cl3]. Some representative mixed-ligand homodinuclear complexes [(X-terpy)Ru(dpqtpy)Ru(Y-terpy)][PF6]4 containing both electron-releasing and electron-withdrawing terminator ligands were prepared from the reaction of [Ru(X-terpy)(dpqtpy)][PF6]2 with an equimolar quantity of [Ru(Y-terpy)Cl3]. The specific examples with mixed terminator ligands were [(terpy)Ru(dpqtpy)Ru(dmterpy)][PF6]4, [(terpy)Ru(dpqtpy)Ru(msterpy)][PF6]4 and [(dmterpy)Ru(dpqtpy)Ru(msterpy)][PF6]4. All of the compounds were fully characterised, and detailed spectroscopic, spectrometric and electrochemical studies are described.