From Organotransition-Metal Chemistry Toward Molecular Electronics: Electronic Communication Between Ligand-Bridged Metals
From Organotransition-Metal Chemistry Toward Molecular Electronics: Electronic Communication Between Ligand-Bridged Metals
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从有机过渡金属化学到分子电子学：配体桥金属之间的电子通信
DOI：
10.1002/chin.199748291
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发表时间：
1997
期刊：
影响因子：
--
通讯作者：
D. Astruc
中科院分区：
文献类型：
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作者：
D. Astruc
过渡金属的分子科学在一个令人着迷的新领域具有潜在的应用：分子电子学。 1, 2 这一希望“尤其”基于以下事实：过渡金属的氧化态可以在很大程度上变化，因此可以产生许多电子转移过程。 2 通过适当的分子工程，应该可以组装和调整包括过渡金属在内的分子器件，并组织它们与宏观世界的界面。光、电子转移和磁光特性之间的相互作用将为未来技术的各种需求提供高效、精确的分子传感器。 1-5在这种情况下，我们希望检查简单双金属模型系统的电子特性以及两种金属之间通过这些分子中的离域桥配体的电子通信。这是本报告的主题，将解决以下问题：(i) 能否设计简单的配体桥接双金属配合物作为分子导体的良好模型？(ii) 哪些因素控制两种金属之间通过离域配体的电子通信？(iii) 在此类系统中单电子和多电子转移的后果和应用是什么？(iv) 烃桥双金属配合物的分子电子学反过来可用于其有机金属化学（即合成、催化和机理研究）？两个氧化还原中心之间的电子转移过程已经用各种连接体进行了研究：简单的无机原子或配体，例如吡嗪、4,4'-联吡啶、6种多烯（包括胡萝卜素）、7种多苯基、8种多炔、9和多芳族化合物。 10 长程电子-
The molecular sciences of the transition metals have potential applications in a new fascinating field: molecular electronics. 1, 2 This hope is based “inter alia” on the fact that the oxidation states of transition metals can be varied to a great extent and thus that many electrontransfer processes can result. 2 By suitable molecular engineering, it should become possible to assemble and tune molecular devices including transition metals and organize their interface with the macroscopic world. The interplay between light, electron transfer, and magnetooptic properties will then provide efficient and precise molecular sensors for the various needs of future technology. 1-5In this context, we wish to examine the electronic properties of simple bimetallic model systems and the electronic communication between the two metals across a delocalized bridging ligand in these molecules. This is the subject of the present Account, which will address the following questions:(i) Can one design simple ligandbridged bimetallic complexes as good models for molecular conductors?(ii) What factors control the electronic communication between the two metals across a delocalized ligand?(iii) What are the consequences and applications of single-and multiple-electron transfers in such systems?(iv) Can the molecular electronics of hydrocarbon-bridged bimetallic complexes be, in turn, useful for their organometallic chemistry (ie, synthesis, catalysis, and mechanistic studies)? Electron-transfer processes between two redox centers have been examined with various linkers: simple inorganic atoms or ligands such as, for instance, pyrazine, 4, 4′-bipyridine, 6 polyenes including-carotene, 7 polyphenyls, 8 polyynes, 9 and polyaromatics. 10 Long-range electron-