Department of Chemistry Graduate School of Science, Tohoku University, 6-3 Aoba, Aramaki, Aoba-Ku, Sendai, Miyagi, 980-8578, Japan.
Emergent Molecular Function Research Team, RIKEN Center for Emergent Matter Science (CEMS), 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
Chem Asian J. 2020 Mar 16;15(6):915-919. doi: 10.1002/asia.201901756. Epub 2020 Feb 26.
We carried out a systematic investigation of packing structures of a series of dimethoxyanthracenes, i. e., 1,4- (1), 1,8- (2), 1,5- (3), 2,6- (4), and 2,7-derivatives (5). The packing structures of the dimethoxyanthracenes are classified into two types, a rubrene-like pitched π-stack (1-3) and a typical herringbone packing (4 and 5), which evidently show that the position of methoxy groups is crucial to determine the packing structure of dimethoxyanthracenes. Effects of the substitution position on intermolecular interactions are analyzed by the noncovalent intermolecular interaction (NCI) method, Hirshfeld surface analysis, and symmetry-adapted perturbation theory (SAPT) method, thus clarifying active roles of the methoxy groups in the formation of rubrene-like pitched π-stack. The present results shed light on a molecular design strategy to realize the rubrene-like pitched π-stack in the solid state, which had been regarded as a packing structure limited for rubrene and its closely related derivatives.
我们对一系列二甲氧基蒽的堆积结构进行了系统的研究，即 1,4-（1）、1,8-（2）、1,5-（3）、2,6-（4）和 2,7-衍生物（5）。二甲氧基蒽的堆积结构分为两种类型，即类似于并五苯的堆积π-堆积（1-3）和典型的鱼骨堆积（4 和 5），这显然表明甲氧基的位置对于确定二甲氧基蒽的堆积结构至关重要。通过非共价分子间相互作用（NCI）方法、Hirshfeld 表面分析和对称自适应微扰理论（SAPT）方法分析了取代位置对分子间相互作用的影响，从而阐明了甲氧基在形成类似于并五苯的堆积π-堆积中的作用。这些结果为在固态中实现类似于并五苯的堆积π-堆积提供了一种分子设计策略，这种堆积结构一直被认为是局限于并五苯及其密切相关衍生物的堆积结构。
