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首页> 外文期刊>Chemistry: A European journal >Synthetic Control of the Excited-State Dynamics and Circularly Polarized Luminescence of Fluorescent 'Push-Pull' Tetrathia[9]helicenes
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Synthetic Control of the Excited-State Dynamics and Circularly Polarized Luminescence of Fluorescent 'Push-Pull' Tetrathia[9]helicenes

机译：荧光“推挽”四方体的激发态动力学和圆偏振发光的合成控制[9]螺旋

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摘要

A series of fluorescent push-pull tetrathia[9]helicenes based on quinoxaline (acceptor) fused with tetrathia[9]helicene (donor) derivatives was synthesized for control of the excited-state dynamics and circularly polarized luminescence (CPL) properties. In this work, introduction of a quinoxaline onto the tetrathia[9]helicene skeleton induced the push-pull character, which was enhanced by further introduction of an electron-releasing Me2N group or an electron-withdrawing NC group onto the quinoxaline unit (denoted as Me2N-QTTH and NC-QTTH, respectively). These trends were successfully discussed in terms of by electrochemical measurements and density functional theory (DFT) calculations. As a consequence, significant enhancements in the fluorescence quantum yields (phi(FL)) were achieved. In particular, the maximum phi(FL) of Me2N-QTTH was 0.43 in benzene (NC-QTTH: phi(FL)=0.30), which is more than 20 times larger than that of a pristine tetrathia[9]helicene (denoted as TTH; phi(FL)=0.02). These enhancements were also explained by kinetic discussion of the excited-state dynamics such as fluorescence and intersystem crossing (ISC) pathways. Such significant enhancements of the phi(FL) values thus enabled us to show the excellent CPL properties. The value of anisotropy factor g(CPL) (normalized difference in emission of right-handed and left-handed circularly polarized light) was estimated to be 3.0x10(-3) for NC-QTTH.
机译：合成了一系列基于喹喔啉（受体）与四硫[9]螺旋（供体）衍生物融合的荧光推挽四硫[9]螺旋，以控制激发态动力学和圆极化发光（CPL）性质。在这项工作中，在四硫[9]螺旋骨架上引入喹喔啉诱导了推挽特性，通过在喹喔啉单元上进一步引入一个释放电子的Me2N基团或一个吸电子NC基团（表示为Me2N-QTTH和NC-QTTH）。通过电化学测量和密度泛函理论（DFT）计算成功地讨论了这些趋势。结果，实现了荧光量子产率（phi（FL））的显着提高。特别是，Me2N-QTTH的最大phi（FL）在苯中为0.43（NC-QTTH：phi（FL）= 0.30），比原始四硫[9] ic烯（表示为）大20倍以上。 TTH; phi（FL）= 0.02）。这些增强还通过动力学讨论激发态动力学来解释，例如荧光和系统间交叉（ISC）途径。 phi（FL）值的如此显着提高因此使我们能够显示出出色的CPL特性。对于NC-QTTH，各向异性因子g（CPL）（右旋和左旋圆偏振光发射的标准化差）的值估计为3.0x10（-3）。

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