通过将带有联苯或联噻吩基团的有机硼氨基喹啉酸酯基双硅氧烷单体与1,4-二乙炔基苯衍生物进行Sonogashira–Hagihara偶联,可以制备通过π共轭桥连接的新型有机硼氨基喹啉酸酯聚合物。所得聚合物中硼原子的四配位态通过11 B NMR光谱证实,并且它们的特征还在于11 H NMR和IR光谱学和尺寸排阻色谱法。通过紫外可见吸收和光致发光光谱学研究了它们的光学性质。在400 nm以上的区域中,与由1.4-二乙炔基-2-全氟辛基-5-三氟甲基苯制备的聚合物相比,由1,4-二乙炔基-2-2,5-二辛氧基苯制备的聚合物表现出红移。具有联苯部分的聚合物显示出更高的绝对荧光量子产率(ϕ F = 0.28和0.65),而具有联噻吩部分的聚合物导致低量子产率的降低(ϕ F= 0.19和0.00)。对应于聚合物的模型化合物的密度泛函理论(DFT)和随时间变化的DFT计算与UV-vis特性的结果非常吻合。
Synthesis of highly luminescent organoboron polymers connected by bifunctional 8-aminoquinolate linkers
作者:Yuichiro Tokoro、Atsushi Nagai、Yoshiki Chujo
DOI:10.1002/pola.24153
日期:2010.8.15
New organoboron aminoquinolate‐based polymerslinked by π‐conjugated bridge were prepared by Sonogashira–Hagihara coupling of organoboron aminoquinolate‐based bisiodo monomers bearing biphenyl or bithiophene moiety with 1,4‐diethynylbenzene derivatives. Tetracoordination states of boron atoms in the obtained polymers were confirmed by 11B NMR spectroscopy, and they were also characterized by 1H NMR
通过将带有联苯或联噻吩基团的有机硼氨基喹啉酸酯基双硅氧烷单体与1,4-二乙炔基苯衍生物进行Sonogashira–Hagihara偶联,可以制备通过π共轭桥连接的新型有机硼氨基喹啉酸酯聚合物。所得聚合物中硼原子的四配位态通过11 B NMR光谱证实,并且它们的特征还在于11 H NMR和IR光谱学和尺寸排阻色谱法。通过紫外可见吸收和光致发光光谱学研究了它们的光学性质。在400 nm以上的区域中,与由1.4-二乙炔基-2-全氟辛基-5-三氟甲基苯制备的聚合物相比,由1,4-二乙炔基-2-2,5-二辛氧基苯制备的聚合物表现出红移。具有联苯部分的聚合物显示出更高的绝对荧光量子产率(ϕ F = 0.28和0.65),而具有联噻吩部分的聚合物导致低量子产率的降低(ϕ F= 0.19和0.00)。对应于聚合物的模型化合物的密度泛函理论(DFT)和随时间变化的DFT计算与UV-vis特性的结果非常吻合。
synthesized optically active organoboron aminoquinolate‐based coordination polymers bearing the chiral side chain derived from L‐alanine, and studied their optical behavior by UV–vis and photoluminescence spectroscopies. Higher absolute quantum yields (ΦF) of the obtained polymers, measured by integrating sphere method, were observed with electron‐withdrawing substituent (ΦF = 0.80) than with electron‐donating