Magnetic Circular Dichroism and Electronic Structure of [Re2X4(PMe3)4]+ (X = Cl, Br)

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• 作者：Diana Habel-Rodriguez ; Frederic Poineau ; Erik V. Johnstone ; Kenneth R. Czerwinski ; Alfred P. Sattelberger ; Martin L. Kirk
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：February 3, 2014
• 年：2014
• 卷：53
• 期：3
• 页码：1260-1262
• 全文大小：205K
• ISSN：1520-510X

文摘

Magnetic circular dichroism (MCD) and electronic absorption spectroscopies have been used to probe the electronic structure of the classical paramagnetic metal鈥搈etal-bonded complexes [Re₂X₄(PMe₃)₄]⁺ (X = Cl, Br). A violation of the MCD sum rule is observed that indicates the presence of ground-state contributions to the MCD intensity. The z-polarized 未 鈫?未* band in the near-IR is formally forbidden in MCD but gains intensity through a combination of ground- and excited-state mechanisms to yield a positive C term.