Deprotonation-Induced Aromaticity Enhancement and New Conjugated Networks in meso-Hexakis(pentafluorophenyl)[26]hexaphyrin
Deprotonation-Induced Aromaticity Enhancement and New Conjugated Networks in meso-Hexakis(pentafluorophenyl)[26]hexaphyrin
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DOI：
10.1002/chem.201200991
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发表时间：
2012-12-01
影响因子：
4.3
通讯作者：
Kim, Dongho
中科院分区：
文献类型：
--
作者：
Cha, Won-Young;Lim, Jong Min;Kim, Dongho
具有26P电子线路的Meso-六(五氟苯基)取代中性六氢呋喃具有相当平坦的分子结构和很强的芳香性，可视为具有18P电子线路的卟啉的真正同系物。我们研究了通过去质子化大环分子腔中的内部N？H基团来增加meso-hexakis(pentafluorophenyl)[26]hexaphyrin(1.1.1.1.1.1)的芳香性，试图诱导进一步的结构平坦化。去质子化的[26]六氢呋喃的单阴离子和双阴离子表现出尖锐的类B带，非常强的荧光，以及长时间的单态和三态激发态，这表明芳香性增强。结构、光谱和计算研究表明，去质子化会引起结构形变，从而导致主共轭p电子回路的改变，并导致芳香性增强。
meso-Hexakis(pentafluorophenyl)-substituted neutral hexaphyrin with a 26p-electronic circuit can be regarded as a real homolog of porphyrin with an 18p-electronic circuit with respect to a quite flat molecular structure and strong aromaticity. We have investigated additional aromaticity enhancement of meso-hexakis(pentafluorophenyl)[26]hexaphyrin(1.1.1.1.1.1) by deprotonation of the inner N?H groups in the macrocyclic molecular cavity to try to induce further structural planarization. Deprotonated mono- and dianions of [26]hexaphyrin display sharp B-like bands, remarkably strong fluorescence, and long-lived singlet and triplet excited-states, which indicate enhanced aromaticity. Structural, spectroscopic, and computational studies have revealed that deprotonation induces structural deformations, which lead to a change in the main conjugated p-electronic circuit and cause enhanced aromaticity.