Highly Near-Infrared Photoluminescence from Aza-Borondipyrromethene-Based Conjugated Polymers
Highly Near-Infrared Photoluminescence from Aza-Borondipyrromethene-Based Conjugated Polymers
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DOI：
10.1002/pola.24335
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发表时间：
2010-12-01
影响因子：
--
通讯作者：
Chujo, Yoshiki
中科院分区：
文献类型：
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作者：
Yoshii, Ryousuke;Nagai, Atsushi;Chujo, Yoshiki
通过钯催化的Sonogashira聚合反应，将二碘苯官能化的氮杂硼二吡咯亚甲基（Aza-BODIPY）单体与1，4-二乙炔基-2，5-二十六烷氧基苯或3，3 '-二十二烷基-2，2'-二乙炔基-5，5 '-联噻吩在Aza-BODIPY核上的3和5或1和7位取代，制备了近红外（NIR）发射共轭聚合物。聚合物的结构通过H-1 NMR、C-13 NMR、B-11 NMR、傅里叶变换红外光谱（FT-IR）和尺寸排阻色谱（SEC）进行了表征。通过紫外-可见吸收光谱和光致发光光谱（PL谱）以及密度泛函理论（DFT）的理论计算，对样品的光学性质进行了表征。该聚合物在四氢呋喃（THF）、邻二甲苯、甲苯、三氯甲烷和二氯甲烷等常见有机溶剂中均易溶和易熔。由于聚合物的p-共轭范围扩大，其紫外-可见吸收光谱和荧光光谱较简单的Aza-BODIPY向长波方向移动。聚合物有效地发射NIR光，在每个吸收最大值处激发时，在713 nm处具有与777 nm相似的窄发射带。特别地，将1，4-二乙炔基-2，5-二十六烷氧基苯连接到核上的3，5-位的聚合物在该NIR区域（753 nm）显示出强烈的量子产率（Phi（F）= 24%）。(C)2010 Wiley Periodicals，Inc.聚合物科学杂志A部分：聚合物化学48：5348-5356，2010
Near-infrared (NIR) emissive conjugated polymers were prepared by palladium-catalyzed Sonogashira polymerization of diiodobenzene-functionalized aza-borondipyrromethene (Aza-BODIPY) monomers, which were substituted at 3 and 5 or 1 and 7 positions on the Aza-BODIPY core, with 1,4-diethynyl-2,5-dihexadecyloxybenzene or 3,3'-didodecyl-2,2'-diethynyl-5,5'-bithiophene. The structures of the polymers were confirmed by H-1 NMR, C-13 NMR, B-11 NMR, Fourier transform infrared (FT-IR) spectroscopies, and size exclusion chromatography (SEC). The optical properties were then characterized by UV-vis absorption and photoluminescence (PL) spectroscopies, and theoretical calculation using density-functional theory (DFT) method. The polymers were fusible and soluble in common organic solvents including tetrahydrofuran (THF), o-xylene, toluene, CHCl3, and CH2Cl2, etc. The UV-vis absorption and PL spectra of the polymers shifted to long wavelength region in comparison with simple Aza-BODIPY as the counterpart because of extended p-conjugation of the polymers. The polymers efficiently emitted NIR light with narrow emission bands at 713 similar to 777 nm on excitation at each absorption maximum. Especially, the polymer attached 1,4-diethynyl-2,5-dihexadecyloxybenzene to 3,5-position on the core revealed intense quantum yields (Phi(F) = 24%) in this NIR region (753 nm). (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 5348-5356, 2010