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Thionine Dye Confined in Zeolite L: Synthesis Location and Optical Properties

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    Thionine Dye Confined in Zeolite L: Synthesis Location and Optical Properties
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    † Dipartimento di Scienze della Terra, Università degli Studi di Torino, Via Valperga Caluso 35, 10125 Torino, Italy
    ‡ Nanostructure Interfaces and Surfaces, Centre of Excellence, Via Quarello 15A, 10135 Torino, Italy
    § Dipartimento di Scienze ad Alta Tecnologia, Università degli Studi dell’Insubria, Via Valleggio, 11, 22100 Como, Italy
    ∥ Dipartimento di Chimica, Università degli Studi di Torino, Via Pietro Giuria 7, 10125 Torino, Italy
    ⊥ Department of Chemistry, University of Fribourg, Chemin du Musée 9, CH-1700 Fribourg, Switzerland
    # Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Modena, Via Giuseppe Campi 103, 41125 Modena, Italy
    *E-mail: [email protected] (R.A.).
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2015, 119, 28, 16156–16165
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    https://doi.org/10.1021/acs.jpcc.5b04717
    Published June 25, 2015
    Copyright © 2015 American Chemical Society
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    Abstract

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    The process of light conversion is at present deeply investigated to develop more efficient devices for artificial photosynthesis, water splitting, photovoltaic applications, and targeting therapeutic agents. This process is induced by nanostructured functional materials, such as zeolites light sensitized by dye molecules adsorbed into their pores. Here a detailed study of the organization of the cationic dye thionine (Th) inserted into the linear 12MR channels of zeolite L is carried out by XRPD, FT-IR spectroscopy—for the determination of the host–guest interactions—and UV–vis absorption and photoluminescence spectroscopies for the investigation of the electronic states of the guest. Two composites with different Th loading (labeled ZL/0.15Th and ZL/0.27Th) were obtained through ion exchange. TGA spectra and IR-ATR spectroscopy clearly indicated penetration of Th molecules into the ZL channels. Rietveld structural refinement showed that Th molecules in both composites are aligned parallel to the 12MR channel axis and located on the mirror planes parallel to the c-axis. Water molecules interact strongly with the dye and form a kind of solvent–matrix tube shaped around the Th molecule, favoring the upright arrangement of the molecules. DR–UV–vis spectra of the ZL/Th composites indicated that Th molecules are hosted in the ZL channels in a monomeric form. Photoluminescence spectroscopy demonstrated that photoluminescent dyes correspond to ca. 5% of the total amount of Th molecules in the zeolite porosities. While most of the photoluminescent Th molecules exhibit a lifetime equivalent to Th in solutions, the complementary fraction of photoluminescent Th exhibit significantly longer lifetimes, resulting from an entrapment in defects of the zeolite structure, inducing strong rotational constraints to the molecules.

    Copyright © 2015 American Chemical Society

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    Supporting Information

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    Observed and calculated diffraction patterns and final difference curve from Rietveld refinements of the pure ZL and of the ZL/0.15Th and ZL/0.27Th composites; atomic coordinates, occupancy factors, and thermal displacement parameters for the ZL/0.15Th, ZL/0.27Th composites; extraframework bond distances for ZL/0.15Th and ZL/0.27Th, composites; the assignment of the various ATR-IR signals of pure compound Th and inside the ZL and bare ZL. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.5b04717.

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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2015, 119, 28, 16156–16165
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpcc.5b04717
    Published June 25, 2015
    Copyright © 2015 American Chemical Society
    Request reuse permissions

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