Fluorescent mesomorphic pyrazinacenes
Fluorescent mesomorphic pyrazinacenes
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DOI：
10.1039/c6tc04628b
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发表时间：
2016-01-01
影响因子：
6.4
通讯作者：
Hill, Jonathan P.
中科院分区：
文献类型：
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作者：
Richards, Gary J.;Ishihara, Shinsuke;Hill, Jonathan P.
我们报告了高荧光吡嗪并苯（6，13-dihydrohexazapentacene; fluorubine）的合成，其在6，13位含有基团，以促进其在非极性有机溶剂中的溶解度和自组装性能。将亲水性3，4，5-三[2-[2-（2-甲氧基乙氧基）乙氧基]乙氧基]苄基（TEG（3）Bz）和疏水性3，4，5-三（1-正十二烷氧基）苄基（C12（3）Bz）基团引入一系列化合物1-9中，其中通过2-溴化或通过引入四个外围苯并基团来修饰氟比因核。因此，1-3分别是亲水性6，1 - 3-（TEG（3）Bz）（2）、疏水性6，1 - 3-（C12（3）Bz）（2）和两亲性6-（TEG（3）Bz）（C12（3）Bz），4-6是相应的2-溴化化合物，7-9是相应的[a，c，l，n]-四苯并化合物。几种化合物表现出热致中间相：4和7甚至在室温下也具有层状结构; 8和9在较高温度下形成柱状矩形相。所有化合物都是高荧光的，在溶液中表现出高达60%的量子产率（QY）。固态荧光光谱显示，虽然未改性的6，1 - 3-二氢六氮杂并五苯化合物1-3在固态下保持其大的QY，但2-溴化（4-6）显著降低了QY（至约10%）。7-9在溶液中得到与1-3类似的QY，但由于发色团聚集，它们的QY在固态下减弱。
We report the synthesis of highly fluorescent pyrazinacenes (6,13-dihydrohexaazapentacene; fluorubine) containing groups at 6,13 positions that promote their solubility in non-polar organic solvents and their self-assembly properties. Hydrophilic 3,4,5-tris[2-[2-(2-methoxyethoxy) ethoxy] ethoxy] benzyl (TEG(3)Bz) and hydrophobic 3,4,5-tris(1-n-dodecyloxy) benzyl (C12(3)Bz) groups were incorporated in a series of compounds 1-9 where the fluorubine core was modified either by 2-bromination or by introduction of four peripheral benzo groups. Thus, 1-3 are respectively hydrophilic 6,13-(TEG(3)Bz)(2), hydrophobic 6,13-(C12(3)Bz)(2) and amphiphilic 6-(TEG(3)Bz)(C12(3)Bz) with 4-6 being the corresponding 2-brominated compounds and 7-9 the corresponding [a, c, l, n]-tetrabenzo compounds. Several of the compounds exhibit thermotropic mesophases: 4 and 7 have lamellar structures even at room temperature; 8 and 9 form columnar rectangular phases at higher temperatures. All the compounds are highly fluorescent exhibiting quantum yields (QY) up to 60% in solution. Solid state fluorescence spectra reveal that while the unmodified 6,13-dihydrohexaazapentacene compounds 1-3 maintain their large QYs in the solid state, 2-bromination (4-6) reduces the QY substantially (to 10% approx.). 7-9 give QY similar to 1-3 in solution but their QYs are attenuated in solid state due to chromophore aggregation.