Efficient Synthesis of Fluorinated Phenanthrene Monomers Using Mallory Reaction and Their Copolymerization
Efficient Synthesis of Fluorinated Phenanthrene Monomers Using Mallory Reaction and Their Copolymerization
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DOI：
10.1021/acs.macromol.6b02151
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发表时间：
2017-01
期刊：
影响因子：
5.5
通讯作者：
Hiroki Fukumoto;Masatoshi Ando;Tomomi Shiota;Hirokazu Izumiya;T. Kubota
中科院分区：
文献类型：
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作者：
Hiroki Fukumoto;Masatoshi Ando;Tomomi Shiota;Hirokazu Izumiya;T. Kubota
1，2-二芳基六氟环戊烯（1，芳基= 3-溴苯基; 2，芳基= 4-溴苯基）在光照射（λ = 365 nm）下在碘化物存在下进行马洛里反应，得到二溴菲衍生物3和4。以9，9-二辛基芴-2，7-二硼酸双（1，3-丙二醇）酯为单体，通过Suzuki-Miyaura偶联法进行缩聚反应，高产率地合成了菲型共聚物Poly-3和Poly-4。为了比较，还类似地制备了二苯基乙烯型共聚物（Poly-1和Poly-2）。Poly-3和Poly-4在二氯甲烷中的紫外-可见光谱分别在380和354 nm处出现π-π* 跃迁峰，在较长的波长处出现了额外的肩峰，表明聚合物分子的分子组装。相比之下，溶液中Poly-1和Poly-2的光谱基本上没有变化，这可能是由于聚合物主链中π-共轭体系的部分中断。聚合物具有光致发光性能。
The Mallory reaction of 1,2-diarylhexafluorocyclopentene (1, aryl = 3-bromophenyl; 2, aryl = 4-bromophenyl) under light irradiation (λ = 365 nm) in the presence of iodide proceeded to give dibromophenanthrene derivatives, 3 and 4. Polycondensation of 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol)ester with the obtained monomers by Suzuki–Miyaura coupling afforded the phenanthrene-type copolymers Poly-3 and Poly-4 in high yields. For comparison, diphenylethene-type copolymers (Poly-1 and Poly-2) were also prepared analogously. UV–vis spectra of Poly-3 and Poly-4 in CHCl3 showed π–π* transition peaks at 380 and 354 nm, respectively, and additional shoulder peaks appeared at a longer wavelength in the film, suggesting the molecular assembly of the polymer molecules. In contrast, the spectra of Poly-1 and Poly-2 in solution were essentially unchanged as measured in the film, presumably owing to partial interruption of the π-conjugation system in polymer main chains. The copolymers showed photolum...