Departamento de Química Física, Universidad del País Vasco, UPV/EHU, Apartado 644, 48080 Bilbao, Spain.
Chemistry. 2013 Jul 22;19(30):9859-65. doi: 10.1002/chem.201301285. Epub 2013 Jun 18.
The fluorescing dye Pyronine Y has been incorporated by crystallization inclusion into three different one-dimensional microporous aluminophosphate host materials. A computer-aided rational choice of the framework of the host material made it possible to modulate the aggregation state of the guest dye molecules. Undesirable H-type dimers of Pyronine Y are included within the large channels of the AFI structure, which allow the inclusion of any of the aggregated species of the dye. Density functional theory (DFT) calculations show that H-type aggregate formation is suppressed within the ATS framework. Experimental results indicate that red-emissive J-type aggregates are formed instead, offering a one-directional, organized, multicolour emission system that is interesting for energy transport. Complete suppression of aggregation is achieved by the inclusion of Pyronine Y within the AEL-type structure, due to its particular topology and channel dimensions This results in a highly fluorescent hybrid system with extraordinarily preferential alignment of the chromophores. Here, we report experimental evidence and modelling insights for how the "cage effect" of the nanochannels can tune the optical properties of the hybrid composite material by influencing the aggregation state of the dye.
荧光染料 Pyronine Y 通过结晶包含被纳入三种不同的一维微孔磷酸铝主体材料中。通过计算机辅助对主体材料的框架进行合理选择，使得调节客体染料分子的聚集态成为可能。不希望出现的 Pyronine Y H 型二聚体被包含在 AFI 结构的大通道中，该通道允许包含染料的任何聚集态。密度泛函理论（DFT）计算表明，在 ATS 框架内抑制了 H 型聚集体的形成。实验结果表明，取而代之的是形成红色发射的 J 型聚集体，提供了一种单向、有序、多色发射系统，这对于能量传递很有趣。通过将 Pyronine Y 包含在 AEL 型结构中，可以完全抑制聚集，这是由于其特殊的拓扑结构和通道尺寸。这导致了具有极高荧光的杂化系统，其中发色团具有非常优先的取向。在这里，我们报告了实验证据和建模见解，说明了纳米通道的“笼效应”如何通过影响染料的聚集态来调节杂化复合材料的光学性质。
