Unsymmetrically Substituted 1,1鈥?Biferrocenylenes Maintain Class III Mixed-Valence Character

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• 作者：Rochus Breuer ; Michael Schmittel
• 刊名：Organometallics
• 出版年：2013
• 出版时间：October 28, 2013
• 年：2013
• 卷：32
• 期：20
• 页码：5980-5987
• 全文大小：380K
• 年卷期：v.32,no.20(October 28, 2013)
• ISSN：1520-6041

文摘

UV鈥搗is鈥搉ear-IR electronic absorption spectra of unsymmetrically substituted derivatives of 1,1鈥?biferrocenylene (bis(fulvalene)diiron = BFD) have been systematically evaluated upon oxidation using spectroelectrochemical techniques. Upon reversible electrochemical oxidation to the BFD⁺ monocation and BFD²⁺ dication state, the characteristic intervalence charge-resonance (IVCR) transitions of a class III mixed-valence system in solution state was confirmed. The class III mixed-valence character of the parent BFD⁺ system was not altered upon unsymmetric substitution. Peak-fit analysis and TD-DFT calculations were utilized to assign the observed IVCR transitions.