基于马鞍形环八四噻吩的复合纳米材料的制备及发光性能

doi:10.19894/j.issn.1000-0518.210101

摘要/Abstract

摘要：

由于环八四噻吩具有独特的“马鞍形”空间结构和光电性质，因此受到越来越多的关注。环八四噻吩（COThs）共有14种同分异构体，其中COTh-1是一类特殊的聚集诱导发光体系，但仅在四氢呋喃等少数有机溶剂中有一定的溶解度，发光强度较弱，限制了这类材料的应用。多孔二氧化硅纳米材料具有比表面积大、孔体积大、粒径可调、生物相容性好、环境友好和表面可功能化等优点，可作为与有机材料复合的最佳选择。本文先用3-氨基丙基-三乙氧基硅烷将COThs功能化，再用溶胶-凝胶法制备COThs-多孔硅复合纳米材料。用傅里叶变换红外光谱、扫描电子显微镜和荧光光谱分别对材料的结构、形貌和发光性质进行了详细的表征。结果表明，COThs分子通过共价键与多孔硅连接，所制备的复合材料呈规则的球形，直径为90～100 nm。与COThs自身相比，复合材料的发光强度显著增强。这可能是由COThs分子在多孔硅的孔道内使得分子内运动受限所致。

关键词: 环八四噻吩, 二氧化硅, 复合纳米材料, 发光性能

Abstract:

Cyclooctatetrathiophenes (COThs) have attracted much attention for their unique "saddle-shaped" space structure, and interesting photoelectric properties. COThs have fourteen isomers and five of them have been reported up to now. COTh-1 exhibits aggregation induced emission properties. More importantly, the mechanism stems from its "saddle-shaped" structure. However, this compound can only be dissolved in few kinds of organic solvent such as tetrahydrofuran, and the low luminescence intensity limits their applications. Porous silica nanomaterials have the advantages of large specific surface area, large pore volume, tunable particle size, good biocompatibility, environmental friendliness and surface functionality. They can be used as good candidates for composing with organic materials. In this work, COTh-1 functionalized with 3-aminopropyltriethoxysilane, then COTh-silica hybrid nanomaterial were prepared by sol-gel method. Their structures, morphology and fluorescence properties were characterized carefully with Fourier transform infrared (FT-IR), scanning electron microscope (SEM) and fluorescence spectrum, respectively. FT-IR results show that COTh-1 molecules are linked on silica via covalent bonds. The morphology of hybrid particle is uniform sphere with size of 90~100 nm. More importantly, the emission intensity of the hybrid material is enhanced unambiguously compared with that of COTh-1. The possible reason is that COTh-1 molecules are fixed within the pores of silica and results in restriction of the intramolecular motions of COTh-1 molecules.

Key words: Cyclooctatetrathiophene, Silica, Hybrid Materials, Fluorescence properties

中图分类号:

O611.1

赵春梅, 周秀苗, 金茜茜, 王雨杭, 党祎静. 基于马鞍形环八四噻吩的复合纳米材料的制备及发光性能[J]. 应用化学, 2022, 39(02): 283-288.

Chun-Mei ZHAO, Xiu-Miao ZHOU, Xi-Xi JIN, Yu-Hang WANG, Yi-Jing DANG. Preparation of Saddle-Shaped Cyclooctatetrathiophene-Based Hybrid Nanomaterials and Fluorescence Properties[J]. Chinese Journal of Applied Chemistry, 2022, 39(02): 283-288.

图/表 4

图1 COTh-1和COTh-2的分子结构

Fig.1 Molecule structures of COTh-1 and COTh-2

图2 COTh-SNP复合材料的合成路线

Fig.2 Synthetic route to COTh-SNP hybrid materials

图3 COTh-APS的FT-IR光谱（A）和COTh-SNP复合材料的SEM照片（B）

Fig.3 FT-IR spectra of COTh-APS（A）and SEM image of COTh-SNP hybrid nanomaterial（B）

图4 COTh-SNP复合材料、COTh-1及COTh+SNP在DMSO中的荧光光谱

Fig.4 Fluorescence spectra of COTh-SNP hybrid nanomaterial，COTh-1 and COTh+SNP in DMSO

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