Guldi Dirk M, Rahman G M Aminur, Sgobba Vito, Ehli Christian
Universität Erlangen, Institute for Physical and Theoretical Chemistry, 91058 Erlangen, Germany.
Chem Soc Rev. 2006 May;35(5):471-87. doi: 10.1039/b511541h. Epub 2006 Mar 6.
This critical review covers the timely topic of carbon nanostructures-fullerenes and carbon nanotubes-in combination with metalloporphyrins as integrative components for electron-donor-acceptor ensembles. These ensembles are typically probed in condensed media and at semi-transparent electrode surfaces. In particular, we will present a comprehensive survey of a variety of covalent (i.e., nanoconjugates) and non-covalent linkages (i.e., nanohybrids) to demonstrate how to govern/fine-tune the electronic interactions in the resulting electron-donor-acceptor ensembles. In the context of covalent bridges, different spacers will be discussed, which range from pure "insulators" (i.e., amide bonds, etc.) to sophisticated "molecular wires" (i.e., p-phenylenevinylene units, etc.). Furthermore, we will elucidate the fundamental impact that these vastly different spacers may exert on the rate, efficiency, and mechanism of short- and long-range electron transfer reactions. Additionally, a series of non-covalent motifs will be described: hydrogen bonding, complementary electrostatics, pi-pi stacking and metal coordination-to name a few. These motifs have been successfully employed by us and our collaborators en route towards novel architectures (i.e., linear structures, tubular structures, rotaxanes, catenanes, etc.) that exhibit unique and remarkable charge transfer features.
这篇批判性综述涵盖了碳纳米结构（富勒烯和碳纳米管）与金属卟啉结合作为电子供体-受体组合体的整合组件这一热门话题。这些组合体通常在凝聚介质和半透明电极表面进行探测。特别是，我们将全面综述各种共价键（即纳米共轭物）和非共价键（即纳米杂化物），以展示如何控制/微调所得电子供体-受体组合体中的电子相互作用。在共价桥的背景下，将讨论不同的间隔基，其范围从纯“绝缘体”（即酰胺键等）到复杂的“分子导线”（即对苯撑乙烯基单元等）。此外，我们将阐明这些截然不同的间隔基可能对短程和长程电子转移反应的速率、效率和机制产生的根本影响。此外，还将描述一系列非共价基序：氢键、互补静电作用、π-π堆积和金属配位等。我们和我们的合作者在构建具有独特且显著电荷转移特性的新型结构（即线性结构、管状结构、轮烷、索烃等）的过程中成功采用了这些基序。
