Orientation and aggregation of cationic laser dyes in a fluoromica: Polarized spectrometry studies

Nobuo Iyi, Ryo Sasai, Taketoshi Fujita, Takahiro Deguchi, Takayuki Sota, Fernando López Arbeloa, Kenji Kitamura

    Research output: Contribution to journalArticle

    68 Citations (Scopus)

    Abstract

    Polarized infrared (IR) and polarized ultraviolet-visible light (UV-VIS) absorption spectra were measured for cationic laser dyes, rhodamine 6G (R6G) and oxazine 4 (Ox4), incorporated in an oriented film of synthetic fluoromica (Li taeniolite, LiTN) to determine the orientation of dye molecules in the interlayer space. Dependence of absorbance on the incident angle of polarized light was observed for characteristic vibrational modes of R6G and Ox4 in the infrared region. It indicated qualitatively that dye molecules were tilted with the longest axis of the condensed ring nearly perpendicular to the host layer (vertical orientation). Polarized UV-VIS spectra showed the absorption of monomer, dimer and high-order aggregates of dyes in the interlayer space of TN. The monomer and dimer absorption bands of the dyes did not show any dependence on the polarized incident light. The dichroic ratio dependence on the incident angle of polarized light was observed for H-aggregates, from which the H-aggregates were calculated to be oriented at 71° for Ox4/TN and 73° for R6G/TN against the layer. The obtained molecular orientation in the interlayer space is consistent with the basal spacings derived from powder X-ray diffraction (PXRD) data-22.4 Å for Ox4/TN and 23.7 Å for R6G/TN. Other states of dyes showed only negligible dependence, implying that interlayer distance is determined by the high-order H-aggregate in the interlayer space. Such vertical orientation was ascribed to the high cation exchange capacity (CEC) of LiTN and the dye aggregation in the interlayer space.

    Original languageEnglish
    Pages (from-to)125-136
    Number of pages12
    JournalApplied Clay Science
    Volume22
    Issue number3
    DOIs
    Publication statusPublished - 2002 Dec

    Fingerprint

    Dye lasers
    Oxazines
    Spectrometry
    spectrometry
    dye
    Coloring Agents
    Agglomeration
    laser
    Light polarization
    Dimers
    Absorption spectra
    Monomers
    Infrared radiation
    Molecules
    Molecular orientation
    X ray powder diffraction
    Light absorption
    absorption spectrum
    Cations
    absorbance

    Keywords

    • Aggregation
    • Intercalation
    • Laser dyes
    • Molecular orientation
    • Polarized spectrometry
    • Synthetic fluoromica

    ASJC Scopus subject areas

    • Geochemistry and Petrology
    • Geology

    Cite this

    Orientation and aggregation of cationic laser dyes in a fluoromica : Polarized spectrometry studies. / Iyi, Nobuo; Sasai, Ryo; Fujita, Taketoshi; Deguchi, Takahiro; Sota, Takayuki; López Arbeloa, Fernando; Kitamura, Kenji.

    In: Applied Clay Science, Vol. 22, No. 3, 12.2002, p. 125-136.

    Research output: Contribution to journalArticle

    Iyi, Nobuo ; Sasai, Ryo ; Fujita, Taketoshi ; Deguchi, Takahiro ; Sota, Takayuki ; López Arbeloa, Fernando ; Kitamura, Kenji. / Orientation and aggregation of cationic laser dyes in a fluoromica : Polarized spectrometry studies. In: Applied Clay Science. 2002 ; Vol. 22, No. 3. pp. 125-136.
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    abstract = "Polarized infrared (IR) and polarized ultraviolet-visible light (UV-VIS) absorption spectra were measured for cationic laser dyes, rhodamine 6G (R6G) and oxazine 4 (Ox4), incorporated in an oriented film of synthetic fluoromica (Li taeniolite, LiTN) to determine the orientation of dye molecules in the interlayer space. Dependence of absorbance on the incident angle of polarized light was observed for characteristic vibrational modes of R6G and Ox4 in the infrared region. It indicated qualitatively that dye molecules were tilted with the longest axis of the condensed ring nearly perpendicular to the host layer (vertical orientation). Polarized UV-VIS spectra showed the absorption of monomer, dimer and high-order aggregates of dyes in the interlayer space of TN. The monomer and dimer absorption bands of the dyes did not show any dependence on the polarized incident light. The dichroic ratio dependence on the incident angle of polarized light was observed for H-aggregates, from which the H-aggregates were calculated to be oriented at 71° for Ox4/TN and 73° for R6G/TN against the layer. The obtained molecular orientation in the interlayer space is consistent with the basal spacings derived from powder X-ray diffraction (PXRD) data-22.4 {\AA} for Ox4/TN and 23.7 {\AA} for R6G/TN. Other states of dyes showed only negligible dependence, implying that interlayer distance is determined by the high-order H-aggregate in the interlayer space. Such vertical orientation was ascribed to the high cation exchange capacity (CEC) of LiTN and the dye aggregation in the interlayer space.",
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    AU - Iyi, Nobuo

    AU - Sasai, Ryo

    AU - Fujita, Taketoshi

    AU - Deguchi, Takahiro

    AU - Sota, Takayuki

    AU - López Arbeloa, Fernando

    AU - Kitamura, Kenji

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    N2 - Polarized infrared (IR) and polarized ultraviolet-visible light (UV-VIS) absorption spectra were measured for cationic laser dyes, rhodamine 6G (R6G) and oxazine 4 (Ox4), incorporated in an oriented film of synthetic fluoromica (Li taeniolite, LiTN) to determine the orientation of dye molecules in the interlayer space. Dependence of absorbance on the incident angle of polarized light was observed for characteristic vibrational modes of R6G and Ox4 in the infrared region. It indicated qualitatively that dye molecules were tilted with the longest axis of the condensed ring nearly perpendicular to the host layer (vertical orientation). Polarized UV-VIS spectra showed the absorption of monomer, dimer and high-order aggregates of dyes in the interlayer space of TN. The monomer and dimer absorption bands of the dyes did not show any dependence on the polarized incident light. The dichroic ratio dependence on the incident angle of polarized light was observed for H-aggregates, from which the H-aggregates were calculated to be oriented at 71° for Ox4/TN and 73° for R6G/TN against the layer. The obtained molecular orientation in the interlayer space is consistent with the basal spacings derived from powder X-ray diffraction (PXRD) data-22.4 Å for Ox4/TN and 23.7 Å for R6G/TN. Other states of dyes showed only negligible dependence, implying that interlayer distance is determined by the high-order H-aggregate in the interlayer space. Such vertical orientation was ascribed to the high cation exchange capacity (CEC) of LiTN and the dye aggregation in the interlayer space.

    AB - Polarized infrared (IR) and polarized ultraviolet-visible light (UV-VIS) absorption spectra were measured for cationic laser dyes, rhodamine 6G (R6G) and oxazine 4 (Ox4), incorporated in an oriented film of synthetic fluoromica (Li taeniolite, LiTN) to determine the orientation of dye molecules in the interlayer space. Dependence of absorbance on the incident angle of polarized light was observed for characteristic vibrational modes of R6G and Ox4 in the infrared region. It indicated qualitatively that dye molecules were tilted with the longest axis of the condensed ring nearly perpendicular to the host layer (vertical orientation). Polarized UV-VIS spectra showed the absorption of monomer, dimer and high-order aggregates of dyes in the interlayer space of TN. The monomer and dimer absorption bands of the dyes did not show any dependence on the polarized incident light. The dichroic ratio dependence on the incident angle of polarized light was observed for H-aggregates, from which the H-aggregates were calculated to be oriented at 71° for Ox4/TN and 73° for R6G/TN against the layer. The obtained molecular orientation in the interlayer space is consistent with the basal spacings derived from powder X-ray diffraction (PXRD) data-22.4 Å for Ox4/TN and 23.7 Å for R6G/TN. Other states of dyes showed only negligible dependence, implying that interlayer distance is determined by the high-order H-aggregate in the interlayer space. Such vertical orientation was ascribed to the high cation exchange capacity (CEC) of LiTN and the dye aggregation in the interlayer space.

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    KW - Polarized spectrometry

    KW - Synthetic fluoromica

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