Redox Chemistry and Functionalities of Conjugated Ferrocene Systems
Redox Chemistry and Functionalities of Conjugated Ferrocene Systems
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DOI：
10.1002/chin.200323221
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发表时间：
2003-06
期刊：
影响因子：
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通讯作者：
H. Nishihara
中科院分区：
文献类型：
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作者：
H. Nishihara
本章概述了有关共轭二茂铁系统的报告，分为以下三类：（1）低聚和聚二茂铁，（2）具有共轭间隔基的二茂铁低聚物和聚合物，以及（3）二茂铁受体共轭化合物。本章回顾了混合价络合物的研究，因此，共轭二茂铁系统的氧化还原性质和功能是一个主要的焦点。特别是，分析的分子内电子相互作用的基础上的邻位相互作用模型，偶氮二茂铁的异构化行为，并在二茂铁醌配合物的质子耦合的分子内电子转移在每个类别中进行了描述。综述了共轭二茂铁体系的基本性质，特别是氧化还原行为的研究进展。合成了多种二茂铁双核混合价配合物，并对其物理性质进行了研究。了解分子内电子转移的机制和动力学在这样的配合物是重要的，在阐明基本概念的发展氧化还原为基础的分子器件。共轭二茂铁体系的下一步研究方向是确定多个氧化还原核之间的分子内电子事件，利用外界刺激控制核间电子转移，以及将二茂铁的氧化还原能力联合收割机结合起来。
Publisher Summary This chapter provides an overview of reports concerning conjugated ferrocene systems in the following three categories: (1) oligo- .and poly-ferrocenylenes, (2) ferrocene oligomers and polymers with conjugated spacers, and (3) ferrocene–acceptor conjugated compounds. The chapter reviews studies of mixed-valence complexes; as a result, the redox properties and functionalities of the conjugated ferrocene systems are a primary focus. In particular, analysis of the intramolecular electronic interaction based on the neighboring-site interaction model, isomerization behavior of azoferrocene, and proton-coupled intramolecular electron transfer in ferrocene–quinone complexes are described in each category. The studies on the fundamental properties, and especially redox behavior, of conjugated ferrocene systems have been surveyed. Various kinds of ferrocene dinuclear mixed-valence complexes have been synthesized and their physical properties investigated. To understand the intramolecular electron-transfer mechanism and dynamics in such complexes is important in elucidating fundamental concepts regarding the development of redox-based molecular devices. The next stage of research on the conjugated ferrocene systems should be to identify the intramolecular electronic events between multiple redox nuclei, to control internuclear electron transfer using external stimuli, and to combine the redox abilities of ferrocene.