二（对 - 二苯并）[40]十环蕃（1.0.0.0.0.1.0.0.0.0）钯配合物：一种弱休克尔38π-芳香大环化合物
Di(p-dibenzi)[40]decaphyrin(1.0.0.0.0.1.0.0.0.0) Pd Complex: A Weakly Hückel 38π-Aromatic Macrocycle.
作者信息
Wang Chengwei, Xu Ling, Rao Yutao, Yin Bangshao, Zhou Mingbo, Song Jianxin, Osuka Atsuhiro
机构信息
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, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, 410081, China.
出版信息
Chem Asian J. 2024 Jan 2;19(1):e202300923. doi: 10.1002/asia.202300923. Epub 2023 Nov 27.
Di(p-benzi)[40]decaphyrin(1.0.0.0.0.1.0.0.0.0) BF complex and tris(p-benzi)[60]pentadecaphyrin(1.0.0.0.0.1.0.0.0.0.1.0.0.0.0) BF complex were synthesized by Suzuki-Miyaura coupling of α,α'-diborylated tetrapyrrole BF -complex with 1,4-diiodobenzene. Bis-BF complex was converted to bis-Pd complex via its free base. Macrocycles bis-BF and tris-BF complex take Möbius topology but are nonaromatic, since the macrocyclic conjugation is disrupted by the locally aromatic 1,4-phenylene units. In contrast, bis-Pd complex is a weakly Hückel 38π-aromatic macrocycle as evinced by its red-shifted, enhanced, and structured Q-like bands and a small electrochemical HOMO-LUMO gap. Interestingly, one 1,4-pheylene part of bis-Pd complex takes a quinonoidal distorted structure and the other takes a usual benzene structure in a figure-eight conformation with Hückel topology.
通过α,α'-二硼化四吡咯BF -配合物与1,4-二碘苯的铃木-宫浦偶联反应合成了二（对苯并）[40]癸卟啉（1.0.0.0.0.1.0.0.0.0）BF配合物和三（对苯并）[60]十五卟啉（1.0.0.0.0.1.0.0.0.0.1.0.0.0.0）BF配合物。双BF配合物通过其游离碱转化为双Pd配合物。大环双BF和三BF配合物具有莫比乌斯拓扑结构，但不是芳香性的，因为大环共轭被局部芳香性的1,4-亚苯基单元破坏。相比之下，双Pd配合物是一种弱休克尔38π芳香大环，其红移、增强和结构化的类Q带以及小的电化学HOMO-LUMO能隙证明了这一点。有趣的是，双Pd配合物的一个1,4-亚苯基部分具有醌型扭曲结构，另一个具有通常的苯结构，呈八字形构象，具有休克尔拓扑结构。
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