Liu Yang, Xu Ling, Rao Yutao, Kim Jinseok, Yin Bangshao, Zhou Mingbo, Oh Juwon, Kim Dongho, Song Jianxin, Osuka Atsuhiro
Key Laboratory of Chemical Biology and Traditional Chinese Medicine (Ministry of Educational of China), Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, Hunan Normal University, Changsha 410081, China.
Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul03722, Korea.
Org Lett. 2023 Nov 17;25(45):8121-8126. doi: 10.1021/acs.orglett.3c03231. Epub 2023 Nov 6.
5,10,23-Trimesityl-substituted [24]hexaphyrin(1.1.0.0.1.0) was synthesized as a stable antiaromatic molecule by base-catalyzed twofold SAr reaction and was reduced to the corresponding [26]hexaphyrin, which was an unstable aromatic molecule because it easily oxidized to the [24]hexaphyrin. The [24]hexaphyrin served as a ligand to give the bis-Pd complex and tris-Rh complex with unique structures. The former complex has two square-planar-coordinated Pd ions bridged by an acetate anion and shows a strong paratropic ring current, while the latter complex has three Rh ions coordinated with two pyrrolic nitrogen atoms and two carbonyl groups, but one carbonyl group is shared with two Rh ions in a unique manner.
通过碱催化的双重亲核芳香取代反应合成了5,10,23-均三甲苯基取代的[24]六卟啉(1.1.0.0.1.0)作为一种稳定的反芳香性分子，并将其还原为相应的[26]六卟啉，该[26]六卟啉是一种不稳定的芳香性分子，因为它很容易氧化为[24]六卟啉。[24]六卟啉作为配体形成了具有独特结构的双钯配合物和三铑配合物。前一种配合物有两个由醋酸根阴离子桥连的平面正方形配位钯离子，并显示出强烈的抗磁环电流，而后一种配合物有三个铑离子与两个吡咯氮原子和两个羰基配位，但其中一个羰基以独特的方式与两个铑离子共享。
