Department of Chemical Engineering, Feng Chia University, Taichung 40724, Taiwan.
Molecules. 2013 Dec 27;19(1):327-41. doi: 10.3390/molecules19010327.
The 1,6- and 1,7-regioisomers of dinitro- (1,6-A and 1,7-A) and diamino-substituted perylene bisimides (1,6-B and 1,7-B), and 1-amino-6-nitro- and 1-amino-7-nitroperylene bisimides (1,6-C and 1,7-C) were synthesized. The 1,6-A and 1,7-A regioisomers were successfully separated by high performance liquid chromatography and characterized by 500 MHz 1H-NMR spectroscopy, and subsequently, their reduction which afforded the corresponding diaminoperylene bisimides 1,6-B and 1,7-B, respectively. On the other hand, the monoreduction of 1,6-A and 1,7-A, giving the asymmetric 1-amino-6-nitro (1,6-C) and 1-amino-7-nitroperylene bisimides (1,7-C), respectively, can be performed by shortening the reaction time from 6 h to 1 h. This is the first time the asymmetric 1,6-disubstituted perylene bisimide 1,6-C is obtained in pure form. The photophysical properties of 1,6-A and 1,7-A were found to be almost the same. However, the regioisomers 1,6-C and 1,7-C, as well as 1,6-B and 1,7-B, exhibit significant differences in their optical characteristics. Time-dependent density functional theory calculations performed on these dyes are reported in order to rationalize their electronic structure and absorption spectra.
1,6- 和 1,7-位二硝基（1,6-A 和 1,7-A）和二氨基取代的苝二酰亚胺（1,6-B 和 1,7-B）以及 1-氨基-6-硝基和 1-氨基-7-硝基苝二酰亚胺（1,6-C 和 1,7-C）被合成。1,6-A 和 1,7-A 区域异构体通过高效液相色谱法成功分离，并通过 500 MHz 1H-NMR 光谱进行了表征，随后，它们的还原分别得到相应的二氨基苝二酰亚胺 1,6-B 和 1,7-B。另一方面，1,6-A 和 1,7-A 的单还原，分别得到不对称的 1-氨基-6-硝基（1,6-C）和 1-氨基-7-硝基苝二酰亚胺（1,7-C），可以通过将反应时间从 6 小时缩短到 1 小时来完成。这是第一次以纯形式获得不对称的 1,6-取代的苝二酰亚胺 1,6-C。发现 1,6-A 和 1,7-A 的光物理性质几乎相同。然而，区域异构体 1,6-C 和 1,7-C 以及 1,6-B 和 1,7-B 在光学特性上表现出显著差异。报道了这些染料的时变密度泛函理论计算，以合理化它们的电子结构和吸收光谱。
