Heteroligated supramolecular coordination complexes formed via the halide-induced ligand rearrangement reaction.
Heteroligated supramolecular coordination complexes formed via the halide-induced ligand rearrangement reaction.
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DOI：
10.1021/ar800025w
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发表时间：
2008-12
影响因子：
18.3
通讯作者：
Mirkin CA
中科院分区：
文献类型：
--
作者：
Oliveri CG;Ulmann PA;Wiester MJ;Mirkin CA
超分子配位化学使研究人员能够合成接近纳米尺度的小酶的高阶结构。通常，这种结构具有高度对称的大环方形或笼形。为了构建模仿酶的复杂识别、催化和变构性质的功能结构，研究人员必须做的不仅仅是合成高度对称的纳米结构。他们还必须同时将不同的功能融入到这些结构中，并学习如何调节它们彼此之间的相对安排。对于超分子化学家来说，设计这样的杂多配位络合物仍然是一个巨大的挑战。本文主要介绍了卤化物诱导的配体重排反应(HILR)的发现和发展。两个结合强度不同的半分子配体与含有卤素离子的d8过渡金属前驱体结合。该反应自发地生成杂多配合物，并且具有高度的模块化和通用性。事实上，它不仅可以用来制备镊子络合物，而且还可以从各种不同的配体和过渡金属离子中快速、定量地形成大环三层/阶梯和长方形的杂寡体络合物。这些结构中官能团A和B之间的相对排列可以使用小的辅助配体如卤化物、一氧化碳和腈进行原位调节。基于这个反应，锌和镁的卟啉部分可以被结合到杂多环或镊子支架中。这些例子展示了功能位点的聚合和界面组装，这些功能位点已知参与了酶的许多过程。它们还显示了这些地点的相对空间和横向距离是如何变化的，在许多情况下是可逆的。研究人员可以使用这种络合物来研究广泛的酶过程，包括催化、分子识别、电子转移和变构信号转移。
Supramolecular coordination chemistry allows researchers to synthesize higher-order structures that approach the nanoscale dimensions of small enzymes. Frequently, such structures have highly symmetric macrocyclic square or cage shapes. To build functional structures that mimic the complex recognition, catalytic, and allosteric properties of enzymes, researchers must do more than synthesize highly symmetric nanoscale structures. They must also simultaneously incorporate different functionalities into these structures and learn how to regulate their relative arrangement with respect to each other. Designing such heteroligated coordination complexes remains a significant challenge for supramolecular chemists. This Account focuses on the discovery and development of a novel supramolecular reaction known as the halide-induced ligand rearrangement (HILR) reaction. Two hemilabile ligands with different binding strengths combine with d8 transition metal precursors that contain halide ions. The reaction spontaneously results in heteroligated complexes and is highly modular and general. Indeed, it not only can be used to prepare tweezer complexes but also allows for the rapid and quantitative formation of heteroligated macrocyclic triple-decker/step and rectangular box complexes from a variety of different ligands and transition metal ions. The relative arrangement between functional groups A and B in these structures can be regulated in situ using small ancillary ligands such as halides, CO, and nitriles. Based on this reaction, zinc- and magnesium-porphyrin moieties can be incorporated into heteroligated macrocyclic or tweezer scaffolds. These examples demonstrate the convergent and cofacial assembly of functional sites that are known to be involved in numerous processes in enzymes. They also show how the relative spatial and lateral distances of these sites can be varied, in many cases reversibly. Researchers can use such complexes to study a wide range of enzymatic processes, including catalysis, molecular recognition, electron transfer, and allosteric signal transfer.
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