Origin of Stacked-Ring Aromaticity
Origin of Stacked-Ring Aromaticity
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DOI：
10.1021/jp900258a
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发表时间：
2009-07-09
影响因子：
2.9
通讯作者：
Aihara, Jun-ichi
中科院分区：
文献类型：
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作者：
Aihara, Jun-ichi
尽管4n pi 轮烯的pi 堆叠二聚体中存在强的反异电流，但它们仍然具有负拓扑共振能（TRE）的反芳香性。两个轮烯分子和 pi 堆叠轮烯二聚体之间的 TRE 差异可用作堆叠环芳香性的实际测量。正如 Corminboeuf 等人所预测的，所有 pi 堆积的 4n pi 轮烯二聚体都表现出明显的堆积环芳香性。相比之下，π-堆叠苯二聚体的整个共轭系统的 TRE 比苯的 TRE 的两倍小得多。对电路对能量和磁性的贡献的分析表明，这种叠环芳香性和双异性是由两个反芳香环堆叠产生的许多 (4n + 2) 位电路产生的。二聚体中形成的四方面负责创建这些 (4n + 2) 位点电路。
Although strong diatropic currents run in the pi-stacked dimers of 4n pi annulenes, they are still antiaromatic with negative topological resonance energies (TREs). The TRE difference between two annulene molecules and the pi-stacked annulene dimer call be used as a practical measure of stacked-ring aromaticity. As predicted by Corminboeuf et aL, all pi-stacked 4n pi annulene dimers exhibit marked stacked-ring aromaticity. In contrast, the TRE for the entire conjugated system of a pi-stacked benzene dimer is much smaller than twice the TRE for benzene. The analysis of circuit contributions to energetic and magnetic properties shows that such stacked-ring aromaticity and diatropicity arise from many (4n + 2)-site circuits created by the stacking of two antiaromatic rings. Tetragonal faces formed in the dimers are responsible for the creation of these (4n + 2)-site circuits.