Synthesis and Characterization of a High-Symmetry Ferrous Polypyridyl Complex: Approaching the 5T2/3T1 Crossing Point for FeII

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• 作者：Lindsey L. Jamula ; Allison M. Brown ; Dong Guo ; James K. McCusker
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：January 6, 2014
• 年：2014
• 卷：53
• 期：1
• 页码：15-17
• 全文大小：183K
• ISSN：1520-510X

文摘

Electronic structure theory predicts that, depending on the strength of the ligand field, either the quintet (⁵T₂) or triplet (³T₁) term states can be stabilized as the lowest-energy ligand-field excited state of low-spin octahedral d⁶ transition-metal complexes. The ³T₁ state is anticipated for second- and third-row metal complexes and has been established for certain first-row compounds such as [Co(CN)₆]^{3鈥?/sup>, but in the case of the widely studied FeII ion, only the 5T₂ state has ever been documented. Herein we report that 2,6-bis(2-carboxypyridyl)pyridine (dcpp), when bound to FeII, presents a sufficiently strong ligand field to FeII such that the 5T₂/3T₁ crossing point of the d6 configuration is approached if not exceeded. The electrochemical and photophysical properties of [Fe(dcpp)₂]2+, in addition to being of fundamental interest, may also have important implications for solar energy conversion strategies that seek to utilize earth-abundant components.}