Chemically Induced Breathing of Flexible Porphyrinic Covalent Cages,The Journal of Organic Chemistry

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Chemically Induced Breathing of Flexible Porphyrinic Covalent Cages
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2017-05-08 00:00:00 , DOI: 10.1021/acs.joc.7b00698
Laetitia Schoepff ₁ , Lucas Kocher ₁ , Stéphanie Durot ₁ , Valérie Heitz ₁

Affiliation

The synthesis of two flexible bis-porphyrin cages 3 and 4, incorporating respectively Zn(II) porphyrins and free-base porphyrins, is reported. In both cages, the four covalent linkers that bind the two porphyrins are functionalized with two 1,2,3-triazolyl ligands. These cages were characterized by NMR and HRMS, and for cage 3 incorporating 1,4-diazabicyclo[2.2.2]octane (DABCO), an X-ray crystallographic structure was obtained. Chemically induced conformational changes are studied and compared to those of two related cages with longer flexible linkers. Binding of four silver(I) ions to the peripheral ligands opens the flattened structures in solution and locks the two porphyrins in a face-to-face disposition. Addition of an excess of acid fully expands the cages due to electrostatic repulsion between the positively charged sites. These two reversible processes allow for a chemically induced breathing of the flexible structures.

中文翻译：

柔性卟啉共价笼的化学诱导呼吸

报道了两个柔性双卟啉笼3和4的合成，分别结合了Zn（II）卟啉和游离碱卟啉。在两个笼子中，结合两个卟啉的四个共价接头被两个1,2,3-三唑基配体官能化。这些笼子的特征是NMR和HRMS，对于笼子3结合1，4-二氮杂双环[2.2.2]辛烷（DABCO），获得X射线晶体结构。研究了化学诱导的构象变化，并将其与两个具有较长柔性接头的相关笼子进行了比较。四个银（I）离子与外围配体的结合打开了溶液中的扁平结构，并将两个卟啉以面对面的方式锁定。由于带正电的位点之间存在静电排斥力，因此添加过量的酸会使笼子完全膨胀。这两个可逆过程允许柔性结构的化学诱导呼吸。

更新日期：2017-05-24

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