发光聚合物与大笼型介孔硅构筑的纳米复合体系的光学性能研究

doi:10.6023/A12090679

化学学报 ›› 2012, Vol. 70 ›› Issue (23): 2425-2432.DOI: 10.6023/A12090679 上一篇下一篇

研究论文

发光聚合物与大笼型介孔硅构筑的纳米复合体系的光学性能研究

张文凯^a, 胡成龙^a, 黄赟赟^a, 章明秋^b, 梁晖^a, 陈旭东^a

a 中山大学化学与化工学院新型聚合物材料设计合成与应用广东省普通高校重点实验室广州 510275;
b 中山大学化学与化工学院聚合物复合材料及功能材料教育部重点实验室广州 510275

投稿日期:2012-09-18 发布日期:2012-11-02
通讯作者: 梁晖, 陈旭东 E-mail:ceslhui@mail.sysu.edu.cn; cescxd@mail.sysu.edu.cn
基金资助:
项目受国家自然科学基金重点(No. 51233008)以及国家自然科学基金(No. 20974124)资助.

Incorporation of Light-emitting Polymer into Large Cage-Type Mesoporous Silica: Toward New Luminescent Nanocomposites

Zhang Wenkai^a, Hu Chenglong^a, Huang Yunyun^a, Zhang Mingqiu^b, Liang Hui^a, Chen Xudong^a

a Institute of Polymer Science, DSAPM Lab, OFCM Institute, Sun Yat-Sen University, Guangzhou 510275;
b Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, Sun Yat-sen University, Guangzhou 510275

Received:2012-09-18 Published:2012-11-02
Supported by:
Project supported by the State Key Program of National Natural Science Foundation of China (No. 51233008) and the National Natural Science Foundation of China (No. 20974124)

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摘要/Abstract

合成了具有规整六方棱柱形貌的大孔笼型介孔硅, 通过液相自组装的方法将共轭聚合物链填入孔中, 制备了无机介孔硅-共轭聚合物的纳米复合物. 并利用SEM, TEM, XRD以及N₂吸附等测试表征了介孔硅和复合物. 通过研究这种介孔硅负载长链共轭聚合物的UV-vis光谱、PL光谱以及发光动力学, 证明了聚合物链的聚集作用受到强烈的抑制而链活动能力减弱, 链间激子的能量分布变窄; 链间激子在介孔受限环境中寿命延长. 激光扫描共聚焦显微镜研究发现复合物硅微粒的发光强度比聚合物聚集体的发光强度高20倍以上. 纳米复合物在高温下仍然保持较高的发光强度, 有效的减少了酮缺陷的产生. 光稳定性测试表明该纳米复合物还具有较高的抗光氧化能力.

关键词: 发光聚合物, 荧光, 纳米复合材料

Light-emitting conjugated polymers confined in mesoporous environment create an opportunity for control of the polymer morphology for design of new functional composite materials with suitable qualities. A novel polyfluorene derivative, poly[N-octylcarbazole-co-9,9'-dioctylfluorene-co-1,3,4-oxadiazole] (PCFOz) was synthesized via Pd-catalyzed Sonogashira reaction in a mixture of 3,6-dibromo-9-octylcarbazole, 2,5-bis-(4-bromo-phenyl)-[1,3,4]-oxadiazole and 2,7-diethyne-9,9'-dioctylfluorene with Pd(PPh₃)₂Cl₂ and CuI as the catalyst. The large cage-like mesoporous silica FDU-12 with hexagonal prism morphology was successfully synthesized and modified with TMCS (trimethylchlorosilane). The composite material was prepared by incorporating PCFOz into FDU-12 via one-step liquid-phase self-assembly method, and then fully characterized by mean of X-ray di?raction, nitrogen physisorption porosimetry, scanning electron microscopy (SEM), transmission electron microscope (TEM) and thermogravimetric analysis. The absorption spectra of composites showed a red-shift and narrower band as compared to pristine film, indicating the polymer chains packing in a special style in the cage type pores with a narrower excitonic energy distribution. PL spectra of composite materials suggested that the cages could incorporate more than one chain but less interchain species formed in cages compared with aggregates in film. The fluorescence decay kinetics observed longer exciton lifetimes in the composites resulting from the reduced exciton mobility and strong torsional distortions. Fluorescence signal from composite materials observed by laser scanning confocal microscope showed 20-times-higher than that obtained from pristine polymer film. Temperature dependence of PL spectra of composites was examined by heating the samples from 40 to 450 K, resulting in less than 10% decrease of PL intensity but no spectra variation for nanocomposites, as compared with 52% decrease of PL intensity accompanying with green-band rising for pristine PCFOz. Photostability tests were performed under the radiation of highly focused UV beams, suggesting that the excitons in the PCFOz within the pores of FDU-12 possessed better environmental stability.

Key words: light-emitting polymer, fluorescence, nanocomposites

引用此文

张文凯, 胡成龙, 黄赟赟, 章明秋, 梁晖, 陈旭东. 发光聚合物与大笼型介孔硅构筑的纳米复合体系的光学性能研究[J]. 化学学报, 2012, 70(23): 2425-2432.

Zhang Wenkai, Hu Chenglong, Huang Yunyun, Zhang Mingqiu, Liang Hui, Chen Xudong. Incorporation of Light-emitting Polymer into Large Cage-Type Mesoporous Silica: Toward New Luminescent Nanocomposites[J]. Acta Chimica Sinica, 2012, 70(23): 2425-2432.

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发光聚合物与大笼型介孔硅构筑的纳米复合体系的光学性能研究

Incorporation of Light-emitting Polymer into Large Cage-Type Mesoporous Silica: Toward New Luminescent Nanocomposites

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