外围准轮烷形成对萘修饰PAMAM树枝形聚合物光物理性质的调控

doi:10.6023/A14100694

化学学报 ›› 2014, Vol. 72 ›› Issue (11): 1157-1163.DOI: 10.6023/A14100694 上一篇下一篇

研究论文

外围准轮烷形成对萘修饰PAMAM树枝形聚合物光物理性质的调控

李婧, 曾毅, 张小辉, 于天君, 陈金平, 李嫕

光化学转换与功能材料重点实验室中国科学院理化技术研究所北京 100190

投稿日期:2014-10-09 发布日期:2014-10-22
通讯作者: 曾毅, 李嫕 E-mail:yili@mail.ipc.ac.cn;zengyi@mail.ipc.ac.cn
基金资助:
项目受科技部国家重点基础研究发展计划(Nos. 2013CB834703, 2013CB834505)和国家自然科学基金(Nos. 21273258, 21173245, 21233011, 21073215)资助.

Regulation of Photophysical Properties for Naphthyl Decorated PAMAM Dendrimers by Pseudorotaxane Formation at Periphery

Li Jing, Zeng Yi, Zhang Xiaohui, Yu Tianjun, Chen Jinping, Li Yi

Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190

Received:2014-10-09 Published:2014-10-22
Supported by:
Project supported by the 973 Program (Grant Nos. 2013CB834703, 2013CB834505) and the National Natural Science Foundation of China (Grant Nos. 21273258, 21173245, 21233011, 21073215).

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摘要/Abstract

合成了1～3代外围修饰萘的聚酰胺-胺(PAMAM)树枝形聚合物Gn-NA, 化合物通过了¹H NMR, ¹³C NMR, MALDI-TOF MS, IR的鉴定. 稳态和时间分辨光物理研究表明, 水溶液(含DMSO 0.3%～0.5%, V/V)中Gn-NA分子内相邻萘基团形成激基缔合物, 猝灭了萘单体的荧光发射, 随代数增加, 对萘单体荧光猝灭作用增强. 向体系中加入葫芦[7]脲(CB[7]), CB[7]与萘形成的准轮烷结构1:1的包结复合物, 1～3代Gn-NA中萘与CB[7]的结合常数分别为768, 887和823 mol^-1·L. 准轮烷结构的形成抑制了分子内激基缔合物的生成, 使单体荧光发射大大增强. 本工作为可调控发光树枝形聚合物的发展提供了一种新的策略.

关键词: PAMAM树枝形聚合物, 葫芦[7]脲, 准轮烷, 光物理性质

Dendrimers are regularly and hierarchically branched synthetic macromolecules with monodispersity, globular shape, interior pockets, and numerous peripherial functionality, which endow them with great potential in miscellaneous applications such as host-guest chemistry, chemosensor, catalysis, drug delivery, microreactor and light-harvesting systems. In the present work, a series of naphthyl terminal-decorated polyamidoamine (PAMAM) dendrimers Gn-NA (n=1～3) and model compound were synthesized. The water-soluble PAMAM backbone was constructed by the classic divergent method and the terminal modification of dendrimers by naphthyl groups was accomplished through a reaction of peripheral amino units with naphthyl succinimidyl ester efficiently. The average functionalization extents of the peripheral groups were 100%, 97% and 93% for G1～G3, respectively. The structures of Gn-NA (n=1～3) were characterized by ¹H NMR, ¹³C NMR, MALDI-TOF mass spectra and IR. Steady state and time-resolved photophysical studies reveal that strong interactions among peripheral naphthyls occur within Gn-NA, resulting in the excimer formation and the naphthyl fluorescence quenching. The quenching efficiency of naphthyl fluorescence increases with increasing generations. The assembly of the peripheral naphthyl group with cucurbit[7]uril (CB[7]) forms a pseudorotaxane with ratio of 1:1 and association constants (an application of B-H equation) of 768, 887 and 823 mol^-1·L from generation 1 to generation 3, respectively. The lifetime of the pseudorotaxane of NA-Model with CB[7] is slightly longer than that of NA-Model, indicating that the formation of pseudorotaxane can reduce the nonradiative decay at a certain degree. The lifetimes of naphthyl group and its pseudorotaxane with CB[7] of Gn-NA were resolved to be 2.5～2.7 and 11.4～11.7 ns, respectively, and the lifetimes of the intramolecular naphthyl excimer of Gn-NA were analyzed to be ca. 17 ns. Combining the results of the remarkably increased lifetime of the naphthyl group in its pseudorotaxane form and those of the NA-Model system, we conclude that the peripheral pseudorotaxane formation depresses both the formation of intramolecular naphthyl excimer and the excited state quenching by solvent, thus enhancing the fluorescence emission of naphthyl dramatically. This study provides a potential strategy for developing controllable light-emitting dendritic system with efficient synthesis and improvable photophysical properties.

Key words: PAMAM dendrimer, cucurbit[7]uril, pseudorotaxane, photophysical property

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李婧, 曾毅, 张小辉, 于天君, 陈金平, 李嫕. 外围准轮烷形成对萘修饰PAMAM树枝形聚合物光物理性质的调控[J]. 化学学报, 2014, 72(11): 1157-1163.

Li Jing, Zeng Yi, Zhang Xiaohui, Yu Tianjun, Chen Jinping, Li Yi. Regulation of Photophysical Properties for Naphthyl Decorated PAMAM Dendrimers by Pseudorotaxane Formation at Periphery[J]. Acta Chimica Sinica, 2014, 72(11): 1157-1163.

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外围准轮烷形成对萘修饰PAMAM树枝形聚合物光物理性质的调控

Regulation of Photophysical Properties for Naphthyl Decorated PAMAM Dendrimers by Pseudorotaxane Formation at Periphery

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