Department of Chemistry, Oxford University, Chemistry Research Laboratory, Mansfield Road, Oxford OX1 3TA, UK.
Nature. 2011 Jan 6;469(7328):72-5. doi: 10.1038/nature09683.
Templates are widely used to arrange molecular components so they can be covalently linked into complex molecules that are not readily accessible by classical synthetic methods. Nature uses sophisticated templates such as the ribosome, whereas chemists use simple ions or small molecules. But as we tackle the synthesis of larger targets, we require larger templates-which themselves become synthetically challenging. Here we show that Vernier complexes can solve this problem: if the number of binding sites on the template, n(T), is not a multiple of the number of binding sites on the molecular building blocks, n(B), then small templates can direct the assembly of relatively large Vernier complexes where the number of binding sites in the product, n(P), is the lowest common multiple of n(B) and n(T) (refs 8, 9). We illustrate the value of this concept for the covalent synthesis of challenging targets by using a simple six-site template to direct the synthesis of a 12-porphyrin nano-ring with a diameter of 4.7 nm, thus establishing Vernier templating as a powerful new strategy for the synthesis of large monodisperse macromolecules.
模板被广泛用于排列分子组件，以便它们可以通过经典的合成方法不易获得的共价键连接成复杂的分子。自然界使用复杂的模板，如核糖体，而化学家则使用简单的离子或小分子。但是，当我们着手合成更大的目标时，我们需要更大的模板-而这些模板本身就具有合成挑战性。在这里，我们表明 Vernier 配合物可以解决这个问题：如果模板上的结合位点数量 n(T)不是分子构建块上的结合位点数量 n(B)的倍数，那么小模板可以指导相对较大 Vernier 配合物的组装，其中产物中的结合位点数量 n(P)是 n(B)和 n(T)的最小公倍数（参考文献 8、9）。我们通过使用简单的六位点模板来指导具有 4.7nm 直径的 12 卟啉纳米环的共价合成，证明了这一概念在具有挑战性的目标的共价合成中的价值，从而确立了 Vernier 模板作为合成大的单分散大分子的一种强大的新策略。
