Surface-Mediated Ring-Opening and Porphyrin Deconstruction via Conformational Distortion,Journal of the American Chemical Society

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Surface-Mediated Ring-Opening and Porphyrin Deconstruction via Conformational Distortion
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-09-02 , DOI: 10.1021/jacs.1c05348
Felix Bischoff ₁ , Alexander Riss ₁ , Georg S Michelitsch ₂ , Jacob Ducke ₁ , Johannes V Barth ₁ , Karsten Reuter _{2,

3} , Willi Auwärter ₁

Affiliation

The breakdown of macrocyclic compounds is of utmost importance in manifold biological and chemical processes, usually proceeding via oxygenation-induced ring-opening reactions. Here, we introduce a surface chemical route to selectively break a prototypical porphyrin species, cleaving off one pyrrole unit and affording a tripyrrin derivative. This pathway, operational in an ultrahigh vacuum environment at moderate temperature is enabled by a distinct molecular conformation achieved via the specific interaction between the porphyrin and its copper support. We provide an atomic-level characterization of the surface-anchored tripyrrin, its reaction intermediates, and byproducts by bond-resolved atomic force microscopy, unequivocally identifying the molecular skeletons. The ring-opening is rationalized by the distortion reducing the macrocycle’s stability. Our findings open a route to steer ring-opening reactions by conformational design and to study intriguing tetrapyrrole catabolite analogues on surfaces.

中文翻译：

通过构象畸变进行表面介导的开环和卟啉解构

大环化合物的分解在多种生物和化学过程中至关重要，通常通过氧化诱导的开环反应进行。在这里，我们引入了一种表面化学途径来选择性地破坏原型卟啉种类，裂解一个吡咯单元并提供三吡啉衍生物。通过卟啉与其铜载体之间的特定相互作用实现的独特分子构象，可以在中等温度的超高真空环境中运行该途径。我们通过键分辨原子力显微镜提供了表面锚定三吡喃、其反应中间体和副产物的原子级表征，明确识别分子骨架。通过降低大环稳定性的畸变使开环合理化。我们的发现开辟了一条通过构象设计引导开环反应和研究表面上有趣的四吡咯分解代谢物类似物的途径。

更新日期：2021-09-22

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