二元溶剂体系对含仲胺基团苝酰亚胺衍生物自组装与光电性能的影响

Effects of Binary Solvent System on Aggregation Behaviors and Photoelectric Properties of Perylene Imide Derivative with Secondary Amine Groups

设计了一种含仲胺基团的苝酰亚胺衍生物N,N-二(2-乙基乙二胺基)-1,6,7,12-四(4-叔丁基苯氧基)-3,4,9,10-苝酰亚胺(B-PDI-1),并采用紫外吸收光谱与荧光光谱研究了B-PDI-1在四氢呋喃(THF)/H_(2)O混合溶剂中的光物理性质;通过扫描电镜(SEM)与X射线粉末衍射(XRD)表征B-PDI-1在THF/H_(2)O中所形成的聚集体形态结构;利用循环伏安法(CV)与Guassion模拟运算研究了其变色机理;使用电化学工作站测定了聚集体的J-V曲线与瞬态光响应,并评估了它的光伏性能。结果表明,B-PDI-1在THF/H_(2)O二元溶剂体系自组装过程中由红色变为蓝色,其紫外吸收光谱则出现了红移现象,在THF含量f THF=10%时达到了最大值35.4 nm,随着THF/H_(2)O二元溶剂体系中THF含量减少,荧光强度将会逐渐降低,但始终存在着微弱的荧光,意味着B-PDI-1具有J型聚集的特征;B-PDI-1在不同THF/H_(2)O比例的混合溶液中都能形成具有明确形貌的聚集体,在不同THF含量的溶液中分别获得了螺旋带状、长斜四边形、棒状、类球形以及长直纳米带等纳米结构;随着该组装体系中THF含量发生变化,分子堆积方式也将改变,分子间的微扰作用集中体现在HOMO能级的提高,由于不同聚集体能带的差异导致了颜色的变化,且在f_(THF)=10%时B-PDI-1的光波转化效率达到最大值(0.43%)。

Aperylene imide derivative N,N-2(2-ethylethylenediamine)-1,6,7,12-4(4-tert-butyl phenylexy)-3,4,9,10-perylene imide(B-PDI-1)containing secondary amine group prepared.The photophysical properties of B-PDI-1 in THF/H_(2)O self-assembly systems with different THF fractions were investigated by UV-vis and fluorescence spectrum.The morphologies and structures of B-PDI-1 in THF/H_(2)O was characterized by SEM and XRD.Cyclic voltammetry(CV)was used to study the influence of binary solvent environment on the electronic structure of aggregates.The electrochemical workstation was used to measure the J-V curve and transient light response of the aggregate,and the photovoltaic perfor-mance was evaluated.The results showed that the absorption of B-PDI-1 in THF/H_(2)O in the UV-vis spectrum showed red-shift phenomenon,and the maximum value reached 35.4 nm when f THF=10%.With the decrease of f THF in the THF/H_(2)O binary solvent system,the fluorescence gra-dually decreased,but there was always a trace fluorescence.B-PDI-1 adopted J-type aggregation in THF/H_(2)O.B-PDI-1 form aggregates with distinct morphologies in mixed solutions with different THF/H_(2)O ratios.In solutions with different f THF,the nanostructures of spiral strip,long oblique quadrilateral,rod shape,spherical shape and long straight nanoribbon are obtained respectively.With the change of f THF,the mole-cular packing mode is changed,and the perturbation between molecules is mainly manifested in the improvement of HOMO energy level.The difference of energy band of different aggregates causes the color change,and the maximum light wave conversion efficiency is 0.43%at f_(THF)=10%.