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[5,5'-亚甲基双(8-羟基喹啉)镓聚合物的合成及其橙红光发射光谱性质]

[Synthesis and spectral properties of polymer of Tis (5, 5'-methylene-bis (8-hydroxy-quinoline) gallium with orange-red light emitting].

作者信息

Guo Hai-bo, Hao Yu-ying, Fan Wen-hao, Zhang Zhi-qiang, Guo Xiao-xia, Xu Bing-she

机构信息

College of Science of Taiyuan University of Technology, Taiyuan 030024, China.

出版信息

Guang Pu Xue Yu Guang Pu Fen Xi. 2009 May;29(5):1358-61.

PMID:19650489
Abstract

A ligand 5,5'-methylene-bis(8-hydroxyquinoline)(Hqq) was synthesized by condensation reaction at low temperature and was subsequently coordinated to gallium ions to prepare the polymer of tis(5,5'-methylene-bis(8-hydroxyquinoline) gallium (Gaqq3)n. Both chemical structure and phase structure of the ligand and complexes were characterized by Infrared absorption spectrum and X-ray diffraction (XRD). The thermal stability of the complexes was studied by thermogravimetry (TG). The photo-physical properties of the complexes were investigated by ultraviolet absorption spectrum (UV), fluorescence excitation spectrum and emission spectrum. The result indicated that (Gaqq3)n is a thermally stable material, whose decomposition temperature is 443.6 degrees C. The ultraviolet absorption bands of (Gaqq3)n are in the range of 250-500 nm, with a relatively strong band tail absorption between 500 and 650 nm, which shows that the band-gap defect states exists in the forbidden band. The fluorescence excitation band of (Gaqq3)n is located at 380-456 nm, and (Gaqq3)n. emits orange-red fluorescence with the emission peak at 568 nm, which shows that the fluorescence emission of (Gaqq3), is mainly attributed to the charge transfer transitions from phenol to ring pyridine ring, while the pi-->pi* transition of benzene ring is deactivated by non-radiative transition, and makes no contribution to fluorescence emission. (Gaqq3)n optical band gap is 2.49 eV. Compared with the fluorescence emission peak of Gaq3, the fluorescence intensity of (Gaqq3), decreases, which is attributed to the distortion of the two quinoline rings connected to the methylene, hence leads to the poor rigidity and coplanarity of (Gaqq3)n, thus affects fluorescence emission intensity. Because of the extending of the molecular conjugation system, pi electron of (Gaqq3)n is more delocalized, resulting in the redshift of fluorescence emission peak (Gaqq3)n is expected to be applied in organic light emitting display and organic photovoltaic devices.

摘要

通过低温缩合反应合成了配体5,5'-亚甲基双(8-羟基喹啉)(Hqq),随后将其与镓离子配位以制备三(5,5'-亚甲基双(8-羟基喹啉)镓(Gaqq3)n聚合物。通过红外吸收光谱和X射线衍射(XRD)对配体和配合物的化学结构和相结构进行了表征。通过热重分析法(TG)研究了配合物的热稳定性。通过紫外吸收光谱(UV)、荧光激发光谱和发射光谱研究了配合物的光物理性质。结果表明,(Gaqq3)n是一种热稳定材料,其分解温度为443.6℃。(Gaqq3)n的紫外吸收带在250-500nm范围内,在500-650nm之间有相对较强的带尾吸收,这表明在禁带中存在带隙缺陷态。(Gaqq3)n的荧光激发带位于380-456nm,(Gaqq3)n发射橙红色荧光,发射峰位于568nm,这表明(Gaqq3)的荧光发射主要归因于从苯酚到环吡啶环的电荷转移跃迁,而苯环的π→π*跃迁通过非辐射跃迁失活,对荧光发射没有贡献。(Gaqq3)n的光学带隙为2.49eV。与Gaq3的荧光发射峰相比,(Gaqq3)的荧光强度降低,这归因于连接到亚甲基的两个喹啉环的扭曲,从而导致(Gaqq3)n的刚性和共面性较差,进而影响荧光发射强度。由于分子共轭体系的扩展,(Gaqq3)n的π电子更加离域,导致荧光发射峰红移。(Gaqq3)n有望应用于有机发光显示器和有机光伏器件。

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