Anthracene-Arrangement-Dependent Emissions of Crystals of 9-Anthrylpyrazole Derivatives

We have designed and synthesized a series of 9-anthrylpyrazole derivatives 1,4-bis(3-(9-anthryl)-1-pyrazolylmethyl)benzene (1), 1-(3-(9-anthryl)-1-pyrazolylmethyl)-4-(5-(9-anthryl)-1-pyrazolylmethyl)benzene (2), 1,4-bis(3-(9-anthryl)-1-pyrazolyl)benzene (3), and 1-(3-(9-anthryl)-1-pyrazolyl)-4-(5-(9-anthryl)-1-pyrazolyl)benzene (4). All compounds formed two types of crystals that exhibited anthracene-arrangement-dependent emission colors. For instance, crystal 1a with strong π-overlap between anthracene moieties exhibited an emission maximum at 515 nm, while 1b with no such interchromophore interactions displayed an emission band at 424 nm. The fluorescence quantum yield (ΦF) measurements showed that the blue-emitting crystals have high quantum yields (ΦF = 0.46 for 1b, 0.90 for 2a, 0.91 for 2b, 0.77 for 3b, and 0.51 for 4a), suggesting their potential as blue emitters in optoelectronics.

本研究设计并合成了一系列9-蒽基吡唑（9-anthrylpyrazole）衍生物，包括1,4-双(3-(9-蒽基)-1-吡唑基甲基)苯（1）、1-(3-(9-蒽基)-1-吡唑基甲基)-4-(5-(9-蒽基)-1-吡唑基甲基)苯（2）、1,4-双(3-(9-蒽基)-1-吡唑基)苯（3）以及1-(3-(9-蒽基)-1-吡唑基)-4-(5-(9-蒽基)-1-吡唑基)苯（4）。所有化合物均可形成两种晶型，其发射颜色依赖于蒽环的排列方式。例如，晶型1a中蒽基团间存在强π重叠，其发射峰最大值位于515 nm；而晶型1b无此类发色团间相互作用，发射峰位于424 nm。荧光量子产率（fluorescence quantum yield, Φ_F）测试结果显示，发蓝光的晶型具有较高的量子产率：1b的Φ_F为0.46，2a为0.90，2b为0.91，3b为0.77，4a为0.51，这表明这类化合物具备作为光电子学领域蓝光发光材料的潜力。