含叔胺基团苝酰亚胺的合成及其自组装性能  

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

作　　者：李丝雨[1,2] 杨新国 王影[1,2] 龙涛 LI Si-yu;YANG Xin-guo;WANG Ying;LONG Tao(College of Materials Science and Engineering,Hunan University,Changsha 410082,Hunan,China;Key Laboratory for Spray Deposition Technology and Application of Hunan province,Hunan University,Changsha 410082,Hunan,China)

机构地区：[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

出　　处：《精细化工》2019年第11期2220-2226,共7页Fine Chemicals

基　　金：国家自然科学基金资助项目（50573019,51273061）;湖南省自然科学基金（2016JJ2027)

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。Two perylene bisimide derivates,N,N-bi(N,N-dimethylethanamino)-1,6,7,12-tetra(4-tertbutylphenoxy)-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.Theπ–πstacking 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 ofπ–πstacking within the nanobelt formed by MDI-PBI was 0.37 nm.The molecular stacking model was obtained according to this result.

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 

分 类 号：O641.3[理学—物理化学]