1,3-Diketone-Based Organoboron Polymers: Emission by Extending π-Conjugation along a Polymeric Ligand
1,3-Diketone-Based Organoboron Polymers: Emission by Extending π-Conjugation along a Polymeric Ligand
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DOI：
10.1021/ma801690d
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发表时间：
2008-11-25
期刊：
影响因子：
5.5
通讯作者：
Chujo, Yoshiki
中科院分区：
文献类型：
--
作者：
Nagai, Atsushi;Kokado, Kenta;Chujo, Yoshiki
人们一直致力于含硼聚合物和低聚物的设计和合成，因为这些聚合物和低聚物在催化、传感器应用和材料科学方面具有潜在的用途。 1 它们的主要合成技术是将硼部分引入聚合物结构的主链和侧基中的连接（例如，聚（对亚苯基硼烷）、2 聚（环二硼烷）、2a、3 聚硼烯、4 聚（硼乙炔）、5 含硼聚合酸、6 聚（硼酸酯）、7 芳基环硼氧烷官能化聚(苯乙烯-共-乙烯基吡啶)，8等)。近年来，借助染料化学，将硼螯合染料掺入聚合物主链或侧链对于电致发光器件、有机场效应晶体管、光伏等应用特别有吸引力。 9 将有机硼喹啉作为电致发光发色团纳入聚合物侧链中，具有高效的发光和良好的稳定性， 10 一直是一些有趣的研究课题。例如，Jäkle 等人。已经证明，新型明确的有机硼喹啉聚合物是通过 8-羟基喹啉和噻吩基取代的聚（硼基苯乙烯）11 的聚合反应制备的，并且通过用取代的 8-羟基喹啉衍生物处理，成功地将有机硼喹啉聚合物的发射颜色从蓝色区域调节到红色区域。 12 随后，Weck 等人。还报道了通过 8-羟基喹啉官能化聚合物合成聚苯乙烯支撑的有机硼喹啉，以使用低成本溶液工艺制造有机发光二极管（OLED）。 13 相比之下，我们报道了将有机硼喹啉集成的 π 共轭聚合物（即主链型有机硼喹啉聚合物）合成到聚合物主链 14 以及进一步的主链型有机硼氨基喹啉聚合物。 15 它们的聚合物具有类似的特性，即强荧光和通过沿聚合物主链延伸 π 共轭而有效地将能量迁移到硼螯合部分。二酮酸硼也是硼螯合染料之一，并且由于摩尔吸收系数大和荧光量子产率 (ΦF) 大而作为荧光团引起了人们的关注。 16 二酮酸硼的共轭是由于酮和烯醇结构之间互变异构形成稳定的六元硼螯合环而通过 OH 伸缩模式抑制非辐射耗散而产生的，并且硼络合物没有丧失二酮酸荧光团的独特特性，例如与重金属络合物相比，高荧光量子产率、高光稳定性。最近，弗雷泽等人。有报道称二氟硼二苯甲酰甲烷
Torrential effort has been devoted to the design and synthesis of boron-containing polymers and oligomers because these polymers and oligomers are potential use in catalysis, sensor applications, and material science. 1 Main synthetic techniques for them are the incorporation of boron moieties into the backbone and the connection in side groups of polymeric structures (eg, poly (p-phenylene-borane) s, 2 poly (cyclodiborazane) s, 2a, 3 polyborole, 4 poly (bora-acetylene) s, 5 boroncontaining polymeric acids, 6 poly (boronate) s, 7 arylboroxinefunctionalized poly (styrene-co-vinylpyridine), 8 etc.). Recently, with the aid to dye chemistry, the incorporation of boronchelating dyes into polymer main chain or side chain is particularly attractive for applications such as electroluminescent devices, organic field-effect transistors, photovoltaics, and so on. 9 The incorporation of organoboron quinolate as an electroluminescent chromophore, possessing efficient luminescence and good stability, 10 into the polymer side chain has been some of the intriguing research topics. For example, Jäkle et al. have demonstrated that novel well-defined organoboron quinolate polymers were prepared by the polymeric reaction of 8-hydroxyquinoline and thienyl-substituted poly (borylstyrene) 11 and have succeeded in the emission color-tunings of the organoboron quinolate polymers from blue to red regions by treatment with substituted 8-hydroxyquinoline derivatives. 12 Subsequently, Weck et al. have also reported the synthesis of polystyrene-supported organoboron quinolate through 8-hydroxyquinoline-functionalized polymers to fabricate organic light-emitting diodes (OLEDs) using a low-cost solution process. 13 In contrast, we reported the synthesis of the π-conjugated polymers integrated organoboron quinolate, ie, main-chaintype organoboron quinolate polymers, into polymer backbone14 and further main-chain-type organoboron aminoquinolate polymers. 15 Their polymers possess analogous properties, that is, strong fluorescence and an efficient energy migration to boronchelating moieties by extending π-conjugation along the polymer backbones.Boron diketonate is also one of boron-chelating dyes and has attracted attention as fluorophores owing to large molar absorption coefficients and large fluorescence quantum yields (ΦF). 16 Conjugation of boron diketonate arises due to inhibition of nonradiative dissipation through OH stretching modes from tautomerization between ketone and enol structures by forming stable six-membered boron-chelating ring, and boron complex has no loss of the unique characteristics of the diketonate fluorophore such as high fluorescence quantum yield, high photostability in contrast with heavy-metal complex. Recently, Fraser et al. have reported that difluoroboron dibenzoylmethane