Pacholska-Dudziak Ewa, Latos-Grażyński Lechosław, Białońska Agata
Department of Chemistry, University of Wroclaw, ul. Joliot-Curie 14, 50-383, Wroclaw, Poland.
Chemistry. 2019 Aug 1;25(43):10088-10097. doi: 10.1002/chem.201901571. Epub 2019 Jul 2.
An aromatic expanded triphyrin, [22]triphyrin(6.6.0) 2, containing a pyrrole unit, a bipyrrole moiety, and annulene links, was obtained from a tellurium-containing precursor meso-tetraaryl-26,28-ditellurasapphyrin 1. The reaction path proceeds through an acid-promoted tellurium extrusion from 1 yielding directly 2, characterized in a dicationic form by X-ray crystallography. In solution the neutral macrocycle 2 reveals flexibility typical for annulenes and it exists as a mixture of conformers that differ by the configuration of the annulene fragments, as proven by H NMR studies and analyzed by DFT methods. The conformation is controlled by protonation state, the nature of an interacting anion, solvent identity, and by interaction with water.
一种芳香族扩展三卟啉，即[22]三卟啉(6.6.0) 2，它含有一个吡咯单元、一个联吡咯部分和轮烯连接键，是由含碲前体中-四芳基-26,28-二碲杂 sapphyrin 1制得的。反应路径是通过酸促进从1中挤出碲，直接生成2，通过X射线晶体学以二价阳离子形式对其进行了表征。在溶液中，中性大环化合物2表现出轮烯典型的柔韧性，它以构象异构体混合物的形式存在，这些构象异构体因轮烯片段的构型不同而有所差异，这已通过1H NMR研究得到证实，并通过密度泛函理论(DFT)方法进行了分析。其构象受质子化状态、相互作用阴离子的性质、溶剂种类以及与水的相互作用控制。
