Highly near‐infrared emissive boron di(iso)indomethene‐based polymer: Drastic change from deep‐red to near‐infrared emission via quantitative polymer reaction
Highly near‐infrared emissive boron di(iso)indomethene‐based polymer: Drastic change from deep‐red to near‐infrared emission via quantitative polymer reaction
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DOI：
10.1002/pola.26547
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发表时间：
2013-04
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影响因子：
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通讯作者：
Ryousuke Yoshii;A. Nagai;Kazuo Tanaka;Y. Chujo
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文献类型：
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作者：
Ryousuke Yoshii;A. Nagai;Kazuo Tanaka;Y. Chujo
从共轭聚合物中实现大亮度和锐利光谱的近红外发射是一项具有挑战性的工作。在这项研究中，我们展示了使用有机硼络合物和聚合后的修饰从聚合物材料中接收强而纯的近红外发射的策略。通过Suzuki-Miyaura偶联反应合成了一系列含硼二(Iso)吲哚(BODIN)和荧烯或联噻吩类的近红外发射共轭聚合物。所得聚合物在深红色到近红外区表现出高发射(量子产率：ΦPL=0.40-0.79，半高全宽：Δλ1/2=660-940 cm-1，发射极大值：λPL=686-714 nm)。其次，对含有邻甲氧基苯基的布丁基聚合物进行了脱甲基化反应。聚合物结构的转变是通过硼原子的中介有效地进行分子内交联来定量进行的。最终，所得聚合物的红移和光致发光光谱都比具有深红光发射的母体聚合物大得多(ΦPL=0.37，Δλ1/2=460 cm-1，λPL=758 nm)。
It is challenging to realize the near-infrared (NIR) emission with large brightness and sharp spectra from the conjugated polymers. In this study, we demonstrate the strategy for receiving strong and pure NIR emission from polymeric materials using organoboron complexes and the modification after polymerization. A series of NIR emissive conjugated polymers with boron di(iso)indomethenes (BODINs) and fluorene or bithiophene were synthesized by Suzuki―Miyaura coupling reaction. The obtained polymers exhibited high emissions in the range from deep-red to NIR region (quantum yields: Φ PL = 0.40-0.79, full width at half maximum height: Δλ 1/2 = 660― 940 cm ―1 , emission maxima: λ PL = 686-714 nm). Next, the demethylation of the BODIN-based polymer with o-methoxyphenyl groups was carried out. The transformation of the polymer structure quantitatively proceeded via efficient intramolecular crosslinking through the intermediary of the boron atom. Finally, the resulting polymer showed both drastically larger red-shifted and sharper photoluminescence spectrum than that of the parent polymer with deep-red emission (Φ PL = 0.37, Δλ 1/2 = 460 cm ―1 , λ PL = 758 nm).