Supramolecular Organization of Dye Molecules in ZeoliteL Channels: Synthesis, Properties, and Composite Materials

• Published in: Chemistry : a European journal Vol. 22; no. 12; pp. 4046 - 4060
• Main Authors: Cao, Pengpeng, Khorev, Oleg, Devaux, Andre, Saegesser, Lucie, Kunzmann, Andreas, Ecker, Achim, Haener, Robert, Bruehwiler, Dominik, Calzaferri, Gion, Belser, Peter
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 14.03.2016; Wiley Subscription Services, Inc
• Subjects: Absorption; Antennas; Channel opening; Channels; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Chromophores; Color; Composite materials; Criteria; Crystals; Design engineering; Diimide; Dyes; Embedded systems; Embedding; Entrances; Fluorescence; Insertion; Intercalation; Nanochannels; Nanostructure; Photochemistry; Physical Sciences; Plugging; Polymer matrix composites; Polymers; Sandwich structures; Science & Technology; Spectra; Stability; Synthesis (chemistry); Trapping; Zeolites; pigments; host-guest systems; ANTENNA SYSTEM; GUEST MOLECULES; COMPLEXES; SOLAR-ENERGY; dyes; L CRYSTALS; MORPHOLOGY CONTROL; zeolites; MICROCRYSTALS; LUMINESCENCE ENHANCEMENT; FRET; ENERGY-TRANSFER; supramolecular chemistry; PERYLENE FLUORESCENT DYES
• DOI: 10.1002/chem.201504404
• ISSN: 0947-6539

Sequential insertion of different dyes into the 1D channels of zeoliteL (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 500nm 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.