Muhammad Nadeem Akhtar, Rahman Bikas, Murad A. AlDamen, Zohreh Shaghaghi, M. Shahid and Andrei Sokolov
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The single crystal X-ray measurements indicated that the cluster is centrosymmetric in structure. The magnetic study demonstrated the presence of very strong antiferromagnetic coupling between the iron centers and the Brillouin fitting showed the best fit with <em>S</em> = 5/2 and <em>g</em> = 1.87. In addition, the water oxidation activity of the cluster has been studied by electrochemical techniques. Electrochemical experiments revealed that the electrode modified by <strong>1</strong> has high efficiency for the oxidation of water and needs an overpotential of 484 mV under a constant current density of 15 mA cm<small><sup>?2</sup></small> with a Tafel slope of 114 mV dec<small><sup>?1</sup></small> in neutral media. Experiments indicated that in the presence of <strong>1</strong>, a yellow solid film was formed on the electrode surface under the applied electrochemical conditions. This yellow material is likely a compound of iron and oxygen and has a crystalline nature. 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引用次数: 4
摘要
氧桥接六核铁簇形成[feii6 (μ4-O)2(edteH)2(piv)4(SCN)4]·2MeCN·2H2O(1)(其中edteH = N,N,N '，N ') -四(2-羟乙基)乙二胺;在KSCN存在下，FeCl2·4H2O与edteH4和piv在CH2Cl2/MeCN中反应合成了piv =戊酸(piv =戊酸)。单晶x射线测量表明，团簇的结构是中心对称的。磁学研究表明，铁中心之间存在很强的反铁磁耦合，当S = 5/2, g = 1.87时，布里渊拟合最佳。此外，还利用电化学技术研究了团簇的水氧化活性。电化学实验表明，1修饰的电极对水的氧化效率高，在恒电流密度为15 mA cm?Tafel斜率为114mv / dec?1在中性介质中。实验表明，在1存在的情况下，在应用的电化学条件下，电极表面形成一层黄色固体膜。这种黄色物质很可能是铁和氧的化合物，具有晶体性质。我们的研究结果表明，随着簇，这种化合物在水氧化反应中是活跃的。
A new hexanuclear Fe(iii) nanocluster: synthesis, structure, magnetic properties, and efficient activity as a precatalyst in water oxidation†
The oxo-bridged hexanuclear iron cluster formulated [FeIII6(μ4-O)2(edteH)2(piv)4(SCN)4]·2MeCN·2H2O (1) (where edteH = N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine; piv = pivalic acid) has been synthesized by the reaction of FeCl2·4H2O with edteH4 and piv in the presence of KSCN in CH2Cl2/MeCN. The single crystal X-ray measurements indicated that the cluster is centrosymmetric in structure. The magnetic study demonstrated the presence of very strong antiferromagnetic coupling between the iron centers and the Brillouin fitting showed the best fit with S = 5/2 and g = 1.87. In addition, the water oxidation activity of the cluster has been studied by electrochemical techniques. Electrochemical experiments revealed that the electrode modified by 1 has high efficiency for the oxidation of water and needs an overpotential of 484 mV under a constant current density of 15 mA cm?2 with a Tafel slope of 114 mV dec?1 in neutral media. Experiments indicated that in the presence of 1, a yellow solid film was formed on the electrode surface under the applied electrochemical conditions. This yellow material is likely a compound of iron and oxygen and has a crystalline nature. Our findings revealed that along with the cluster, this compound is active in water oxidation reactions.
期刊介绍：
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.
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