General Design Strategy of Anti-aromatic Porphyrinoids

被引:3
|
作者
Zhan, Xiaoning [1 ]
Jin, Yucheng [1 ]
Qi, Dongdong [1 ]
Sun, Tingting [1 ]
Jiang, Jianzhuang [1 ]
机构
[1] Univ Sci & Technol Beijing, Dept Chem, Beijing Key Lab Sci & Applicat Funct Mol & Crysta, Beijing 100083, Peoples R China
关键词
anti-aromaticity; computational; heteroatoms; porphyrinoids; ring currents; INDEPENDENT CHEMICAL-SHIFTS; INDUCED CURRENT-DENSITY; ONE-POT SYNTHESIS; QUANTUM CONTRIBUTIONS; AROMATICITY; DELOCALIZATION; NICS; HEPTAPHYRINS; ANISOTROPY; TOPOLOGY;
D O I
10.1002/chem.202201125
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A systematic investigation to arrange the typical anti-aromatic porphyrinoids in sequence was performed. Based on density functional theory calculations, six rules are summarized to obtain the high-performance anti-aromatic porphyrinoids: (1) when two atoms are deleted/added on the 18 pi electron current ring flowing pipe, we will immediately obtain a 16 pi/20 pi electron anti-aromatic system; (2) it is a good idea to increase the number of pyrrole/thiophen/furan units on the pi-electron current ring flowing pipe; (3) the heteroatom selecting order is -O- (optimal choice), -NH- (second choice), and -S- (last choice); (4) it is worth noting that the C-C=C-C unit is not beneficial for the anti-aromatic properties; (5) it is very significant to avoid the crowded environment in the core space of an anti-aromatic molecule. In this view, -O- is much better than -S- and -NH-; (6) the "circular" skeleton is much better than an "ellipse-like", "rectangular", or "parallelogram-like" one.
引用
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页数:20
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