Guo Zongxia, Wang Kun, Yu Ping, Wang Xiangnan, Lan Shusha, Sun Kai, Yi Yuanping, Li Zhibo
Key Laboratory of Biobased Polymer Materials, Shandong Provincial Education Department, School of Polymer Science and Engineering, Qingdao University of Science and Technology (QUST), Qingdao, 266042, P.R. China.
Beijing National Laboratory for Molecular Science (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P.R. China.
Chem Asian J. 2017 Nov 2;12(21):2827-2833. doi: 10.1002/asia.201700984. Epub 2017 Oct 11.
The effect of the length of linear alkyl chains substituted at imine positions on the assembly of tetrachlorinated perylene bisimides (1: PBI with -C H ; 2: PBI with -C H ) has been investigated. Solvent-induced assembly was performed in solutions of THF and methanol with varying volume ratios. Morphological (SEM, AFM, and TEM) and spectral (UV/Vis, fluorescence, FTIR, and XRD) methods were used to characterize the assembled nanostructures and the molecular arrangement in the aggregates. It was found that uniform structures could be obtained for both molecules in solutions with a high ratio of methanol. PBI 1 formed rigid nanosheets, whereas 2 assembled into longer nanostripes with a high ratio of length to width. On combining the morphological data with the spectral data, it was suggested that π-π stacking predominated in assemblies of 1, and the synergetic effect of van der Waals interactions from the long alkyl chains and π-π stacking between neighboring building blocks facilitated the growth of the long-range-ordered nanostructures of 2. By changing the linear chain length, the hierarchical assembly of PBIs modified on bay positions could be manipulated effectively.
研究了亚胺位置取代的线性烷基链长度对四氯化苝双酰亚胺（1：带有-C₆H₁₃的苝双酰亚胺；2：带有-C₈H₁₇的苝双酰亚胺）组装的影响。在具有不同体积比的四氢呋喃和甲醇溶液中进行溶剂诱导组装。采用形态学方法（扫描电子显微镜、原子力显微镜和透射电子显微镜）和光谱学方法（紫外/可见光谱、荧光光谱、傅里叶变换红外光谱和X射线衍射）对组装的纳米结构和聚集体中的分子排列进行表征。结果发现，在甲醇比例较高的溶液中，两种分子都能形成均匀的结构。苝双酰亚胺1形成刚性纳米片，而苝双酰亚胺2组装成长度与宽度比很高的更长纳米带。将形态学数据与光谱学数据相结合表明，在苝双酰亚胺1的组装中π-π堆积占主导，长烷基链的范德华相互作用与相邻结构单元之间的π-π堆积的协同效应促进了苝双酰亚胺2的长程有序纳米结构的生长。通过改变线性链长度，可以有效地操控在湾区位置修饰的苝双酰亚胺的分级组装。
