Schubert Ulrich S, Eschbaumer Christian
Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, The Netherlands.
Angew Chem Int Ed Engl. 2002 Aug 16;41(16):2892-926. doi: 10.1002/1521-3773(20020816)41:16<2892::AID-ANIE2892>3.0.CO;2-6.
The ability of a broad range of N-heterocycles to act as very effective and stable complexation agents for several transition metal ions, such as cobalt(II), copper(II), nickel(II), and ruthenium(II), has long been known in analytical chemistry. This behavior was later utilized in supramolecular chemistry for the construction of highly sophisticated architectures, such as helicates, racks, and grids. The discovery of macromolecules by Staudinger in 1922 opened up avenues towards sophisticated materials with properties hitherto completely unknown. In the last few decades, the combination of macromolecular and supramolecular chemistry has been attempted by developing metal-complexing and metal-containing polymers for a wide variety of applications that range from filtration to catalysis. The stability of the polymer-metal complex is a fundamental requirement for such applications. In this respect, the use of bi- and terpyridines as chelating ligands is highly promising, since these molecules are known to form highly stable complexes with interesting physical properties with transition-metal ions. A large number of different structures have been designed for many different applications, but polymers based on the application of coordinative forces have been prepared in a few cases only. Furthermore, the synthetic procedures applied frequently resulted in low yields. During the last few years, strong efforts have been made in the direction of self-assembling and supramolecular polymers as novel materials with "intelligent" and tunable properties. In this review, an overview of this active area at the interface of supramolecular and macromolecular chemistry is given.
在分析化学领域,人们早就知道多种氮杂环能够作为钴(II)、铜(II)、镍(II)和钌(II)等多种过渡金属离子非常有效且稳定的络合剂。后来,这种特性在超分子化学中被用于构建高度复杂的结构,如螺旋配合物、支架和网格。1922年施陶丁格发现大分子,为开发具有前所未知特性的复杂材料开辟了道路。在过去几十年里,人们尝试将大分子化学和超分子化学结合起来,开发用于从过滤到催化等广泛应用的金属络合聚合物和含金属聚合物。聚合物 - 金属络合物的稳定性是此类应用的基本要求。在这方面,使用联吡啶和三联吡啶作为螯合配体非常有前景,因为已知这些分子能与过渡金属离子形成具有有趣物理性质的高度稳定络合物。为许多不同应用设计了大量不同结构,但仅在少数情况下制备了基于配位作用的聚合物。此外,常用的合成方法往往产率较低。在过去几年中,人们朝着自组装和超分子聚合物这一具有“智能”和可调特性的新型材料方向做出了巨大努力。在这篇综述中,对超分子化学和大分子化学界面这一活跃领域进行了概述。