Cao Pengpeng, Khorev Oleg, Devaux André, Sägesser Lucie, Kunzmann Andreas, Ecker Achim, Häner Robert, Brühwiler Dominik, Calzaferri Gion, Belser Peter
Department of Chemistry, University of Fribourg, Ch. du Musée 9, 1700, Fribourg, Switzerland.
Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, 3012, Bern, Switzerland.
Chemistry. 2016 Mar 14;22(12):4046-60. doi: 10.1002/chem.201504404. Epub 2016 Feb 11.
Sequential insertion of different dyes into the 1D channels of zeolite L (ZL) leads to supramolecular sandwich structures and allows the formation of sophisticated antenna composites for light harvesting, transport, and trapping. The synthesis and properties of dye molecules, host materials, composites, and composites embedded in polymer matrices, including two- and three-color antenna systems, are described. Perylene diimide (PDI) dyes are an important class of chromophores and are of great interest for the synthesis of artificial antenna systems. They are especially well suited to advancing our understanding of the structure-transport relationship in ZL because their core fits tightly through the 12-ring channel opening. The substituents at both ends of the PDIs can be varied to a large extent without influencing their electronic absorption and fluorescence spectra. The intercalation/insertion of 17 PDIs, 2 terrylenes, and 1 quaterrylene into ZL are compared and their interactions with the inner surface of the ZL nanochannels discussed. ZL crystals of about 500 nm in size have been used because they meet the criteria that must be respected for the preparation of antenna composites for light harvesting, transport, and trapping. The photostability of dyes is considerably improved by inserting them into the ZL channels because the guests are protected by being confined. Plugging the channel entrances, so that the guests cannot escape into the environment is a prerequisite for achieving long-term stability of composites embedded in an organic matrix. Successful methods to achieve this goal are described. Finally, the embedding of dye-ZL composites in polymer matrices, while maintaining optical transparency, is reported. These results facilitate the rational design of advanced dye-zeolite composite materials and provide powerful tools for further developing and understanding artificial antenna systems, which are among the most fascinating subjects of current photochemistry and photophysics.
将不同染料依次插入L型沸石（ZL）的一维通道中会形成超分子夹心结构，并能够形成用于光捕获、传输和俘获的复杂天线复合材料。本文描述了染料分子、主体材料、复合材料以及嵌入聚合物基质中的复合材料（包括双色和三色天线系统）的合成与性质。苝二亚胺（PDI）染料是一类重要的发色团，在人工天线系统的合成中备受关注。它们特别适合于增进我们对ZL中结构-传输关系的理解，因为其核心能够紧密地穿过12元环通道开口。PDI两端的取代基可以在很大程度上变化而不影响其电子吸收光谱和荧光光谱。比较了17种PDI、2种并四苯和1种四并苯插入ZL的情况，并讨论了它们与ZL纳米通道内表面的相互作用。使用了尺寸约为500 nm的ZL晶体，因为它们满足制备用于光捕获、传输和俘获的天线复合材料时必须遵循的标准。将染料插入ZL通道中可显著提高染料的光稳定性，因为客体被限制在其中而得到保护。堵塞通道入口以使客体无法逸出到环境中是实现嵌入有机基质中的复合材料长期稳定性的先决条件。描述了实现这一目标的成功方法。最后，报道了在保持光学透明性的同时将染料-ZL复合材料嵌入聚合物基质中的情况。这些结果有助于合理设计先进的染料-沸石复合材料，并为进一步开发和理解人工天线系统提供有力工具，而人工天线系统是当前光化学和光物理中最引人入胜的课题之一。
