Bonding and uneven charge distribution in infinite pyrene π-stacks
Bonding and uneven charge distribution in infinite pyrene π-stacks
复制标题
无限芘叠堆中的键合和不均匀电荷分布
DOI：
10.1039/d2ce00933a
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发表时间：
2022
期刊：
影响因子：
3.1
通讯作者：
Kertesz, Miklos
中科院分区：
文献类型：
--
作者：
Flynn, Chase;Zhou, Zheng;McCormack, Megan E.;Wei, Zheng;Petrukhina, Marina A.;Kertesz, Miklos
在一种新的芘（Py）电荷转移盐（Py）2+（Ga 2Cl 7）−中观察到了不寻常的分子间π堆积。通过单晶X射线晶体学获得的结构表明芘的π-堆叠，其使用密度泛函理论和在不同电荷状态下芘分子中的键长交替模式的分析相结合来分析。在文献中，芘的电荷转移盐的晶体结构相对较少，这种结构显示出独特的电荷分离，其中一半的芘几乎是中性的，而另一半则以交替的方式沿着1D堆叠，平衡一个电子电荷转移到每个（Ga 2Cl 7）−阴离子。电荷局域化归因于单占据分子轨道的不完全的芘间重叠。
Unusual intermolecular π-stacking in a new charge transfer salt of pyrene (Py), (Py)2+(Ga2Cl7)−, has been observed. The structure obtained by single crystal X-ray crystallography indicates π-stacks of pyrene which were analyzed using a combination of density functional theory and the analysis of the bond length alternation patterns in the pyrene molecules in different charge states. There are relatively few crystal structures of charge transfer salts of pyrene in the literature, and this structure shows a unique charge separation in which half of the pyrenes are nearly neutral while the other half carry approximately +1 charge in an alternating fashion along the 1D stacks balancing one electron charge transfer to each (Ga2Cl7)− anion. The charge localization is attributed to the incomplete inter-pyrene overlap of the singly occupied molecular orbitals.