Page 72 - 《精细化工》2019年第11期

第 36 卷第 11 期 精 细 化 工 Vol.36, No.11
2019 年 11 月 FINE CHEMICALS Nov. 2019

电子化学品
含叔胺基团苝酰亚胺的合成及其自组装性能

李丝雨 1,2 ，杨新国 1,2* ，王 影 1,2 ，龙 涛 1,2

（1. 湖南大学 材料科学与工程学院，湖南 长沙 410082；2. 湖南省喷射沉积技术及应用重点实验室，
湖南 长沙 410082）

摘要：利用苝酐为原料，合成了两种不同碳链长度叔胺基取代的苝酰亚胺分子 N,N-二（N,N-二甲基乙二胺基）
-1,6,7,12-四（4-叔丁基苯氧基）-3,4,9,10-苝四甲酸酰亚胺（MDI-PBI）和 N,N-二（3-二甲胺基丙胺基）-1,6,7,12-
四（4-叔丁基苯氧基）-3,4,9,10-苝四甲酸酰亚胺（MPI-PBI），两分子分别在两种两相溶剂体系中进行快速溶剂
扩散自组装。利用 SEM、UV-Vis、偏光干涉和 XRD 对聚集体形貌结构、光物理性能和内部分子排列情况进行
了表征。结果表明，两分子在甲醇中的溶解度(S)比在正己烷中大，且 S(MPI-PBI)＜S(MDI-PBI)。MDI-PBI 和
MPI-PBI 在两种自组装体系中均为 J 型聚集，疏溶剂化作用较强时，分子形成聚集程度更高、更稳定的纳米带
或纳米线；疏溶剂化作用较弱时，形成球状结构。π–π 堆积作用为 MDI-PBI 聚集体长轴方向生长的作用力，疏溶
剂作用为短轴方向生长的作用力，叔胺取代基碳链更长的 MPI-PBI 则刚好相反。V（甲醇）∶V（THF）=5∶1 情
况下 MDI-PBI 形成的纳米带内部分子之间 π–π 堆积的距离为 0.37 nm，并根据此结果得到了其内部分子的堆积模型。
关键词：苝酰亚胺；自组装；快速溶剂扩散法；1D 纳米材料；J 型聚集；分子堆积；电子化学品
中图分类号：O641.3 文献标识码：A 文章编号：1003-5214 (2019) 11-2220-07

Synthesis and Self-assembly Properties of Perylene Bisimide
Modified with Tertiary Amino Groups

1,2
1,2
1,2
LI Si-yu , YANG Xin-guo 1,2* , WANG Ying , LONG Tao
（1. College of Materials Science and Engineering, Hunan University, Changsha 410082, Hunan, China; 2. Key
Laboratory for Spray Deposition Technology and Application of Hunan province, Hunan University, Changsha 410082,
Hunan, China）
Abstract: Two perylene bisimide derivates, N,N-bi(N,N-dimethylethanamino)-1,6,7,12-tetra(4-tert-
butylphenoxy)-perylene-3,4,9,10-tetracarboxylic diimide (MDI-PBI) and N,N-bi[3-(dimethylamino)-1-propyl]-
1,6,7,12-tetra(4-tert-butylphenoxy)-perylene-3,4,9,10-tetracarboxylic diimide (MPI-PBI) were synthesized
from perylene anhydride and tertiary amines with different alkyl chain lengths, and then self assembled in
different two-phase solvent systems by rapid solution dispersion. To investigate the influences of molecular
structure and assembly environment on the self-assembly of MDI-PBI and MPI-PBI, the morphology,
photophysical properties and internal molecular arrangement of aggregates were characterized by SEM,
UV-Vis, POM and XRD. The results showed that the solubility (S) of these two molecules in methanol was
larger than that in n-hexane, and S(MPI-PBI)<S(MDI-PBI). MDI-PBI and MPI-PBI formed J-type
aggregates in two self-assembly systems. Stronger the solvophobic effect was, more stable nanobelts or
nanowires with higher degree of aggregation the molecules formed, while molecules formed spherical
structure when the solvophobic effect was weak in the self-assembly environment. The π–π stacking was
responsible for the elongation of nanobelts formed by MDI-PBI with respect to their long axis while
elongation in short axis direction was caused by solvophobic, which was just contrary to MPI-PBI. When
V(methanol)∶V(THF) was 5∶1, the distance of π–π stacking within the nanobelt formed by MDI-PBI was
0.37 nm. The molecular stacking model was obtained according to this result.

收稿日期：2019-03-19; 定用日期：2019-04-22; DOI: 10.13550/j.jxhg.20190215
基金项目：国家自然科学基金资助项目（50573019，51273061）；湖南省自然科学基金（2016JJ2027）
作者简介： 李丝雨（1995—），女，硕士生，E-mail：lisiyu199512@163.com。联系人：杨新国（1969—），男，副教授，E-mail：
xgyang@hnu.edu.com。