Aromatic Ring-Fused BODIPY-Based Conjugated Polymers Exhibiting Narrow Near-Infrared Emission Bands
Aromatic Ring-Fused BODIPY-Based Conjugated Polymers Exhibiting Narrow Near-Infrared Emission Bands
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DOI：
10.1021/ma901449c
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发表时间：
2010-01-12
期刊：
影响因子：
5.5
通讯作者：
Chujo, Yoshiki
中科院分区：
文献类型：
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作者：
Nagai, Atsushi;Chujo, Yoshiki
以1，4-二乙炔基-2，5-二十六烷氧基苯和三种二碘苯基稠合的BODIPY单体为原料，通过钯催化的Sonogashira偶联反应，合成了三种主链上由对苯乙炔基和硼二（异）吲哚亚甲基单元交替组成的共轭共聚物。通过H-1 NMR、B-11 NMR、FT-IR、元素分析、体积排阻色谱、紫外-可见吸收光谱、光致发光光谱以及密度泛函理论计算等手段对聚合物的结构和性能进行了表征。所得聚合物在THF、苯、甲苯、CHCl_3、CH_2Cl_2等常用有机溶剂中均能溶融。吲哚亚甲基单体引入对苯乙炔基主链后，聚合物的紫外吸收光谱和荧光光谱均发生红移。因此，共聚物在从深红色到近红外区域的范围内发射，发射光谱最大值在约691-720 nm处，并表现出高量子产率（Phi（F）= 33-49%）。通过在有氧条件下使用UV灯在连续UV照射下监测PL光谱的降低来检查聚合物的光稳定性。此外，还通过TGA测量研究了它们的热稳定性。
Three Conjugated copolymers, consisted of alternating p-phenylene-ethynylene and boron di(iso)indomethene units ill the backbone, were synthesized via palladium-catalyzed Sonogashira coupling reaction of 1,4-diethynyl-2,5-dihexadecyloxybenzene and three diiodophenyl-fused BODIPY monomers. The structures and properties of the conjugated polymers were characterized by H-1 NMR, B-11 NMR, and Fourier transform infrared (FT-IR) spectroscopies, elemental analysis, size exclusion chromatography (SEC), UV-vis absorption spectroscopy, photoluminescence (PL) spectroscopy,and theoretical calculation using density-functional theory (DFT) method. The polymers obtained were fusible and soluble in common organic solvents including THF, benzene, toluene, CHCl3, and CH2Cl2, etc, The incorporation of the indomethene monomers into p-phenylene-ethynylene main chain led to red shifts in UV-absorption and PL spectra by extended pi-conjugation of the copolymers in comparison with the monomers. Accordingly, the copolymers emitted in the range from deep-red to near-infrared region with emission spectral maxima at around 691-720 nm and exhibited high quantum yields (Phi(F) = 33-49%). The photostabilities of the polymers were examined by monitoring decrease of the PL spectra Under continuous UV irradiation using a UV lamp under aerobic conditions. Further, their thermal stabilities were also investigated by TGA measurement.