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RETURN TO ISSUEPREVC: Physical Properti...C: Physical Properties of Materials and InterfacesNEXT

Adsorption-Induced Fluorescence of Pseudoisocyanine Monomers in Systems with Layered Silicates

  • Peter Boháč*
    Peter Boháč
    Institute of Inorganic Chemistry, Slovak Academy of Sciences, BratislavaSK-845 36, Slovak Republic
    Centre of Excellence for Advanced Materials Application, Slovak Academy of Sciences, BratislavaSK-845 11, Slovak Republic
    *Email: [email protected]
  • Šimon Budzák
    Šimon Budzák
    Department of Chemistry, Matej Bel University, Banská BystricaSK-974 01, Slovak Republic
  • Viktória Planetová
    Viktória Planetová
    Institute of Inorganic Chemistry, Slovak Academy of Sciences, BratislavaSK-845 36, Slovak Republic
    Department of Chemistry, Matej Bel University, Banská BystricaSK-974 01, Slovak Republic
  • Róbert Klement
    Róbert Klement
    FunGlass─Centre for Functional and Surface Functionalized Glass, TrenčínSK-911 50, Slovak Republic
  • , and 
  • Juraj Bujdák
    Juraj Bujdák
    Institute of Inorganic Chemistry, Slovak Academy of Sciences, BratislavaSK-845 36, Slovak Republic
    Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University in Bratislava, BratislavaSK-842 15, Slovak Republic
Cite this: J. Phys. Chem. C 2022, 126, 40, 17255–17265
Publication Date (Web):October 3, 2022
https://doi.org/10.1021/acs.jpcc.2c03497
Copyright © 2022 American Chemical Society

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    Abstract

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    Interaction of organic dyes with layered silicates can cause various changes in dye properties, such as metachromasia (color change), fluorescence quenching, resonance energy transfer, or even fluorescence enhancement. These phenomena are caused by the molecular aggregation or adsorption of dye molecules on silicate particles. The present work studied the photophysical properties of pseudoisocyanine (PIC) in colloidal dispersions of five samples of layered silicates (smectites) at variable PIC/smectite loadings. The silicates of variable composition and layer charge included one synthetic saponite, one synthetic hectorite, two synthetic Laponites, and one montmorillonite. Chemometric analysis of the absorption spectra revealed the formation of four spectral species: monomers and three types of molecular aggregates exhibiting light absorption in both H- and J-band regions. In addition, the samples of hybrid systems with silicates of lower layer charge under the condition of the lowest PIC/silicate ratio (0.01 mmol g–1) exhibited strong fluorescence surpassing that of J-aggregates. The luminescent species achieving quantum yields of about 50% were assigned to the adsorbed PIC monomers, a phenomenon that has never been observed for this dye. Theoretical calculations found that in water solution bending of the molecule supports nonradiative deactivation of the excited state of the free molecule. Adsorption of PIC molecules on the surface of silicate particles caused the change of the dihedral angle between pyridine subunits, which hinders the nonradiative deactivation channel and favors emission. Fluorescence from adsorbed monomers exhibited a maximum at ≈535 nm, which is at significantly lower wavelengths with respect to the J-aggregates emitting at ≈570 nm and thus cannot be related to dye aggregation as supported by the fact that this phenomenon occurs only at the lowest surface concentrations of the dye.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpcc.2c03497.

    • Excitation of oscillator number 39, i.e., aromatic rings breathing, together with two low-energy oscillators 2 and 3, both corresponding to mutual movements of PIC subunits (MP4)

    • Concentrations of the spectral components measured after 24 h as determined by MCR analysis, calculated values of QY, fluorescence spectra of all samples, and vibronic components (PDF)

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    Cited By

    This article is cited by 1 publications.

    1. Juraj Bujdák, Tímea Šimonová Baranyaiová, Peter Boháč, Róbert Mészáros. Adsorption of Dye Molecules and Its Potential for the Development of Photoactive Hybrid Materials Based on Layered Silicates. The Journal of Physical Chemistry B 2023, 127 (5) , 1063-1073. https://doi.org/10.1021/acs.jpcb.2c07814