收稿日期: 2017-04-18
网络出版日期: 2020-09-03
基金资助
国家自然科学基金资助项目(21401127);上海市自然科学基金资助项目(14ZR1416300)
Electron transfer of water-soluble perylene diimide compound and long-life radical anion generation
Received date: 2017-04-18
Online published: 2020-09-03
利用紫外可见吸收光谱研究了一种结构新颖的以聚乙二醇(polyethylene glycol,PEG)链为取代基的水溶性苝酰亚胺化合物N,N'-二(聚乙二醇)-1-(4-巯基苯)苝酰亚胺(N,N '-Di(polyethylene glycol)-1-(4-mercaptobenzene)-perylene-3,4,9,10-tetracarboxylic diimide, BFL)的聚集行为,溶剂极性、表面活性剂对聚集行为有显著影响。结果表明：在水溶液中BFL在530 nm只出现一个与单体聚集体比例相关的特征峰;浓度增加,溶液中聚集体比例增加不明显;而有机溶剂和表面活性剂能够分散化合物,明显提高单体的数量。在水溶液中硫化钠使BFL发生电子转移反应,能够捕捉到超长寿命的中间产物一价阴离子自由基,之后BFL进一步被还原为二价阴离子。这种能够在还原反应中产生超长寿命自由基的特性使BFL成为优异的n型材料。
程正敏, 张俊, 邢菲菲, 朱守荣 . 水溶性苝酰亚胺化合物电子转移与长寿命自由基阴离子的生成[J]. 上海大学学报(自然科学版), 2020 , 26(4) : 570 -577 . DOI: 10.12066/j.issn.1007-2861.2218
A novel water-soluble perylene diimide compound, N,N'-di(polyethylene glycol)-1-(4-mercaptobenzene)-perylene-3,4,9,10-tetracarboxylic diimide (BFL), was synthesized by introducing PEG chains. Solvent-and temperature-dependent visible spectra were investigated and aggregation states were analysed. The results show that BFL in aqueous solution has only one absorption band at 530 nm, which is related to the ratio of monomer/aggregates. However, the change in the monomer/aggregates ratio with increasing concentration of BFL molecules is not obvious. Organic solvents and surfactants can disperse the compound, thereby significantly increasing the amount of the monomer. BFL can react with sodium sulfide in water;BFL is first reduced to anion radicals and then to dianions. The ability to produce a long-life free radical in the reduction reaction will make the BFL an excellent n-type material.
Key words： perylene diimide; PEG chains; electron transfer; anion radical
| [1] | Gorl D, Zhang X, Wurthner F. Molecular assemblies of perylene bisimide dyes in water[J]. Angewandte Chemie: International Edition, 2012,51(26):6328-6348. |
| [2] | Wurthner F, Sahamoeller C R, Fimmel B, et al. Perylene bisimide dye assemblies as archetype functional supramolecular materials[J]. Chemical Review, 2016,116(3):962-1052. |
| [3] | Kozma E, Catellani M. Perylene diimides based materials for organic solar cells[J]. Dyes and Pigments, 2013,98(1):160-179. |
| [4] | Gao B X, Li H X, Liu H M, et al. Water-soluble and fluorescent dendritic perylene bisimides for live-cell imaging[J]. Chemical Communications, 2011,47(13):3894-3896. |
| [5] | Kavery E, Nagarajan N, Paramaguru G, et al. Synjournal, characterization and binding interactions of amino acids coupled perylene diimides with colloidal doped and undoped TiO$_{2}$[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2015,146:13-23. |
| [6] | Quintana J A, Villalvilla J M, Pena D L, et al. Singular temperatures connected to charge transport mechanism transitions in perylene bisimides from steady-state photocurrent measurements[J]. Journal of Physical Chemistry C, 2015,119(25):14023-14028. |
| [7] | Tang T, Peneva K, Muellen K, et al. Photophysics of water soluble perylene diimides in surfactant solutions[J]. Journal of Physical Chemistry A, 2007,111(42):10609-10614. |
| [8] | Ajayakumar M R, Asthana D, Mukhopadhyay P. Core-modified naphthalenediimides generate persistent radical anion and cation: new panchromatic nir probes[J]. Organic Letters, 2012,14(18):4822-4825. |
| [9] | 高薇, 席亚楠, 薄福丽, 等. 水溶性苝酰亚胺功能荧光染料的合成与性质[J]. 河北大学学报 (自然科学版), 2016,36(2):1000-1565. |
| [10] | Zhong L N, Xing F F, Shi W, et al. Synjournal, spectra, and electron-transfer reaction of aspartic acid-functionalized water-soluble perylene bisimide in aqueous solution[J]. ACS Applied Materials & Interfaces, 2013,5(8):3401-3407. |
| [11] | Ford W E. Photochemistry of 3,4,9,10-perylenetetracarboxylic dianhydride dyes: visible absorption and fluorescence of the di(glycyl)imide derivative monomer and dimer in basic aqueous solutions[J]. Journal of Photochemistry, 1987,37(1):189-204. |
| [12] | Wang J, Zhong S, Duan W, et al. Fluorinated perylene diimides: synjournal, electrochemical-photophysical properties, and cellular imaging[J]. Tetrahedron Letters, 2015,56(6):824-827. |
| [13] | Che Y, Datar A, Yang X, et al. Enhancing one-dimensional charge transport through intermolecular $\pi $-electron delocalization: conductivity improvement for organic nanobelts[J]. Journal of American Chemical Society, 2007,129(20):6354-6355. |
/
| 〈 |
|
〉 |
