Department of Chemistry, Università degli Studi di Milano and INSTM RU, via Golgi 19, 20133 Milano, Italy.
Institute of Molecular Science and Technologies (ISTM) of CNR and INSTM RU, via Golgi 19, 20133 Milano, Italy.
Molecules. 2019 Jul 13;24(14):2552. doi: 10.3390/molecules24142552.
Organic room temperature persistent luminescence is a fascinating but still largely unexplored phenomenon. Cyclic-triimidazole and its halogenated (Br, I) derivatives have recently revealed as intriguing phosphors characterized by multifaceted emissive behavior including room temperature ultralong phosphorescence (RTUP) associated with the presence of H-aggregates in their crystal structure. Here, we move towards a multicomponent system by incorporating a fluoropyridinic fragment on the cyclic-triimidazole scaffold. Such chromophore enhances the molecular properties resulting in a high photoluminescence quantum yield (PL QY) in solution but preserves the solid-state RTUP. By means of X-ray diffraction (XRD) analysis, theoretical calculations, steady-state and time-resolved spectroscopy on solutions, polymethylmethacrylate (PMMA) blends and crystals, the nature of the different radiative deactivation channels of the compound has been disclosed. In particular, the molecular fluorescence and phosphorescence, this latter observed in frozen solution and in PMMA blends, are associated to deactivation from S and T respectively, while the low energy RTUP, observed only for crystals, is interpreted as originated from H aggregates.
有机室温持续发光是一种引人入胜但仍在很大程度上未被探索的现象。环状三咪唑及其卤化(Br、I)衍生物最近被揭示为具有多方面发光行为的有趣磷光体,包括与晶体结构中 H-聚集体存在相关的室温超长磷光(RTUP)。在这里,我们通过在环状三咪唑骨架上引入氟吡啶片段向多组分系统迈进。这种发色团增强了分子性质,导致溶液中的光致发光量子产率(PL QY)很高,但保持了固态 RTUP。通过 X 射线衍射(XRD)分析、理论计算、溶液、聚甲基丙烯酸甲酯(PMMA)共混物和晶体的稳态和时间分辨光谱,揭示了化合物不同辐射去活化通道的性质。特别是,化合物的分子荧光和磷光,后者在冷冻溶液和 PMMA 共混物中观察到,分别与 S 和 T 的去活化有关,而仅在晶体中观察到的低能量 RTUP,则解释为源于 H 聚集体。