Long-Range Intramolecular Electronic Communication in Bis(ferrocenylethynyl) Complexes Incorporating Conjugated Heterocyclic Spacers: Synthesis, Crystallography, and Electrochemistry

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• 作者：Hakikulla H. Shah ; Rayya A. Al-Balushi ; Mohammed K. Al-Suti ; Muhammad S. Khan ; Christopher H. Woodall ; Kieran C. Molloy ; Paul R. Raithby ; Thomas P. Robinson ; Sara E. C. Dale ; Frank Marken
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：May 6, 2013
• 年：2013
• 卷：52
• 期：9
• 页码：4898-4908
• 全文大小：544K
• 年卷期：v.52,no.9(May 6, 2013)
• ISSN：1520-510X

文摘

A new series of bis(ferrocenylethynyl) complexes, 3鈥?b>7, and a mono(ferrocenylethynyl) complex, 8, have been synthesized incorporating conjugated heterocyclic spacer groups, with the ethynyl group facilitating an effective long-range intramolecular interaction. The complexes were characterized by NMR, IR, and UV鈥搗is spectroscopy as well as X-ray crystallography. The redox properties of these complexes were investigated using cyclic voltammetry and spectroelectrochemistry. Although there is a large separation of 14 脜 between the two redox centers, 螖E_1/2 values in this series of complexes ranged from 50 to 110 mV. The appearance of intervalance charge-transfer bands in the UV鈥搗is鈥搉ear-IR region for the monocationic complexes further confirmed effective intramolecular electronic communication. Computational studies are presented that show the degree of delocalization across the Fc鈥揅鈮鈥揅鈮鈥揊c (Fc = C₅H₅FeC₅H₄) highest occupied molecular orbital.