Microscopic organization of long-chain rhodamine molecules in monolayers at the air/water interface

Valeria Tsukanova, Hugo Lavoie, Akira Harata, Teiichiro Ogawa, Christian Salesse

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    Abstract

    The monolayer behavior of a rhodamine derivative with two C18 aliphatic chains attached to the nitrogen atoms of the xanthene ring system (RhC18) was studied by epifluorescence microscopy, second-harmonic generation (SHG), and absorption and fluorescence spectroscopy. The isotherm of RhC18 exhibits a plateau which, presumably, corresponds to a slow collapse of the monolayer. As observed by epifluorescence microscopy, the RhC18 monolayer remained homogeneous for a large range of molecular areas, and an abrupt change in the monolayer morphology occurred at the end of the surface pressure isotherm. Spectroscopic data showed that both fluorescent J-aggregates and nonfluorescent H-aggregates with a coplanar-inclined configuration were formed within the RhC18 monolayer upon compression. The orientational SHG measurements revealed that, in the expanded region of the isotherm, the RhC18 chromophore was oriented in a way where its xanthene plane made an angle of 36° with respect to the interface. The azimuthal angle SHG measurements revealed that compression induced an anisotropic arrangement of the S0-S1 transition moment of RhC18 chromophores perpendicular to the compression direction. At the end of the isotherm prior to and after the collapse point, the film possessed a fairly regular structure characterized by a C2v symmetry packing and a long-range order in the parallel alignment of the RhC18 chromophores. Microscopic organization of the RhC18 molecules in monolayers is discussed.

    Original languageEnglish
    Pages (from-to)4203-4213
    Number of pages11
    JournalJournal of Physical Chemistry B
    Volume106
    Issue number16
    DOIs
    Publication statusPublished - Apr 25 2002

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    All Science Journal Classification (ASJC) codes

    • Physical and Theoretical Chemistry
    • Surfaces, Coatings and Films
    • Materials Chemistry

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