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Supramolecular Assembly‐Improved Triplet–Triplet Annihilation Upconversion in Aqueous Solution
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2018-10-17 , DOI: 10.1002/chem.201804001 Wei Xu 1 , Wenting Liang 2 , Wanhua Wu 1 , Chunying Fan 1 , Ming Rao 1 , Dan Su 1 , Zhihui Zhong 1 , Cheng Yang 1
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2018-10-17 , DOI: 10.1002/chem.201804001 Wei Xu 1 , Wenting Liang 2 , Wanhua Wu 1 , Chunying Fan 1 , Ming Rao 1 , Dan Su 1 , Zhihui Zhong 1 , Cheng Yang 1
Affiliation
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Water‐soluble 9,10‐diphenylanthracene‐modified γ‐cyclodextrin derivatives A1 and A2, in which the γ‐cyclodextrin unit serves as a molecular host for a binding sensitizer, and the 9,10‐diphenylanthracene moiety plays a role as an emitter/annihilator, were synthesized to investigate the supramolecular triplet–triplet annihilation (TTA) upconversion in aqueous solution. Both A1 and A2 readily aggregate and form nanoscale assemblies in water as a combined result of host–guest complexation and π–π stacking among the 9,10‐diphenylanthracenes. The aggregation behavior of the supramolecular emitters was fully characterized by using a diversity of methods, including dynamic light scattering (DLS), SEM, NMR, fluorescence, and circular dichroism studies. Fluorescence spectroscopic analysis reveals that the emitters have high fluorescence quantum yields in water (82 and 90 % for A1 and A2, respectively), thus demonstrating that aggregation does not quench the fluorescence. By using a coordinated ruthenium sensitizer, a high TTA upconversion quantum yield of up to 6.9 % was observed for this supramolecular TTA system, which is significantly higher than the value (<0.5 %) obtained with nonassembled emitters in organic solvent and in contrast to the fact that TTA upconversion emission in aqueous solution is usually low or negligible. We ascribe the strong TTA upconversion emission in the present supramolecular assembly system to an efficient TTA process, which is facilitated along the stacked emitters by triplet energy migration and improved triplet–triplet energy transfer through host–guest complexation.
中文翻译：
超分子组装-改进的三重态-三重态ni灭在水溶液中的上转换
水溶性9,10-二苯基蒽修饰的γ-环糊精衍生物A1和A2，其中γ-环糊精单元充当结合敏化剂的分子主体，而9,10-二苯基蒽部分则充当发射体/合成了ator灭剂，以研究水溶液中的超分子三重态-三重态an灭（TTA）上转换。无论A1和A2宿主-客体络合和9,10-二苯基蒽之间的π-π堆积的综合结果很容易在水中聚集并形成纳米级组装体。超分子发射体的聚集行为已通过多种方法进行了充分表征，包括动态光散射（DLS），SEM，NMR，荧光和圆二色性研究。荧光光谱分析表明，发射体在水中具有很高的荧光量子产率（A1和A2分别为82％和90％，分别），从而证明聚集不会猝灭荧光。通过使用配位钌敏化剂，对于该超分子TTA系统，观察到高达6.9％的高TTA上转换量子产率，这大大高于在有机溶剂中非组装发射体所获得的值（<0.5％）。水溶液中TTA上转换发射的事实通常很少或可以忽略不计。我们将当前的超分子组装系统中强大的TTA上转换发射归因于有效的TTA过程，该过程通过三重态能量迁移和通过主体-客体复合物改善的三重态-三重态能量传递而沿着堆叠的发射极得以促进。
更新日期：2018-10-17
中文翻译：
超分子组装-改进的三重态-三重态ni灭在水溶液中的上转换
水溶性9,10-二苯基蒽修饰的γ-环糊精衍生物A1和A2，其中γ-环糊精单元充当结合敏化剂的分子主体，而9,10-二苯基蒽部分则充当发射体/合成了ator灭剂，以研究水溶液中的超分子三重态-三重态an灭（TTA）上转换。无论A1和A2宿主-客体络合和9,10-二苯基蒽之间的π-π堆积的综合结果很容易在水中聚集并形成纳米级组装体。超分子发射体的聚集行为已通过多种方法进行了充分表征，包括动态光散射（DLS），SEM，NMR，荧光和圆二色性研究。荧光光谱分析表明，发射体在水中具有很高的荧光量子产率（A1和A2分别为82％和90％，分别），从而证明聚集不会猝灭荧光。通过使用配位钌敏化剂，对于该超分子TTA系统，观察到高达6.9％的高TTA上转换量子产率，这大大高于在有机溶剂中非组装发射体所获得的值（<0.5％）。水溶液中TTA上转换发射的事实通常很少或可以忽略不计。我们将当前的超分子组装系统中强大的TTA上转换发射归因于有效的TTA过程，该过程通过三重态能量迁移和通过主体-客体复合物改善的三重态-三重态能量传递而沿着堆叠的发射极得以促进。
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