Shadow Mask Templates for Site-Selective Metal Exchange in Magnesium Porphyrin Nanorings.
Shadow Mask Templates for Site-Selective Metal Exchange in Magnesium Porphyrin Nanorings.
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DOI：
10.1002/anie.201804787
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发表时间：
2018-06
影响因子：
--
通讯作者：
Pernille S Bols;H. Anderson
中科院分区：
文献类型：
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作者：
Pernille S Bols;H. Anderson
分子模板可以以许多不同的方式用于控制化学反应的结果。在此，我们提出了一种新型的模板导向合成。我们表明，模板可以用作阴影掩模：模板的形状成为印记的产品，因为反应只发生在网站不被模板掩盖。当用酸处理镁卟啉纳米环时，我们通过使用寡吡啶模板来指定脱金属位点来证明这种效应。与模板配位的镁中心被保护，而未配位的镁中心被去除。在位点选择性脱金属后，可以除去模板，并且可以将其他阳离子如锌（II）和铜（II）插入游离碱卟啉中心。这种策略提供了一个简单的路线，以广泛的杂金属卟啉阵列。
Molecular templates can be used in many different ways to control the outcome of chemical reactions. Herein, we present a new type of template-directed synthesis. We show that templates can be used as shadow masks: The shape of the template becomes imprinted on the product because reactions only occur at sites not masked by the template. We demonstrate this effect by using oligopyridine templates to dictate the sites of demetalation when a magnesium porphyrin nanoring is treated with acid. Magnesium centers that are coordinated to the template are protected whereas uncoordinated magnesium centers are removed. After site-selective demetalation, the template can be removed, and other cations, such as zinc(II) and copper(II), can be inserted into the free-base porphyrin centers. This strategy provides a simple route to a wide range of heterometalated porphyrin arrays.