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Excited-state intramolecular proton transfer on 2-(2′-hydroxy-4′-R-phenyl)benzothiazole nanoparticles and fluorescence wavelength depending on substituent and temperature

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Abstract

The fluorescence emission properties of 2-(2′-hydroxy-4′-R-phenyl)benzothiazole (HBT-R) nanoparticles with different substituents (R =-COOH,-H,-CH3,-OH, and-OCH3) were investigated using spectroscopic and theoretical methods. HBT-Rs displayed dual enol and keto (excited-state intramolecular proton transfer (ESIPT)) emissions in nonpolar solvents. The spectral change of their ESIPT emissions was affected differently by the electron donating (or withdrawing) power of the substituents; a bathochromic shift for the electron donating group and a hypsochromic shift in electron withdrawing group. In addition, the changes in energy levels calculated by the ab initio method were consistent with the spectral shifts of HBT-R in solution. We prepared aggregated HBT-R nanoparticles using a simple reprecipitation process in tetrahydrofuran-water solvents. The ESIPT emission of aggregated HBT-R nanoparticles was strongly enhanced (over 45 times) compared to those of monomer HBT-Rs in toluene, as markedly shifted ESIPT emissions are observed at longer wavelength without any quenching by self-absorption. Aggregated HBT-R nanoparticles showed longer lifetimes than those of monomer molecules. The temperature effect on the aqueous dispersion of the aggregated HBT-R nanoparticles was also explored. It shows a fluorescent ratiometric change in a range of temperature from 7 to 65 °C. A mechanism of a temperature-dependent equilibrium between the nanoparticles and the solvated enols is proposed for the emission color change.

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Authors and Affiliations

  1. BT Convergence Technology Research Department, ETRI, Daejeon, 305-700, Korea

    Yong Hee Kim, Sang-Don Jung & Myung-Ae Chung

  2. Optical Material Institute, Shindae Specialities Co. Ltd., Daejeon, 305-380, Korea

    Soo-Gyun Roh

  3. Department of Advanced Materials Chemistry, Korea University, Sejong Campus, Chungnam, 339-700, Korea

    Hwan Kyu Kim & Dae Won Cho

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  1. Yong Hee Kim
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Correspondence to Yong Hee Kim or Dae Won Cho.

Additional information

Electronic supplementary information (ESI) available: HOMO and LUMO orbital diagrams, absorption spectra of naonoparticles, and temperature-dependent emission spectra. See DOI: 10.1039/b9pp00102f

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Kim, Y.H., Roh, SG., Jung, SD. et al. Excited-state intramolecular proton transfer on 2-(2′-hydroxy-4′-R-phenyl)benzothiazole nanoparticles and fluorescence wavelength depending on substituent and temperature. Photochem Photobiol Sci 9, 722–729 (2010). https://doi.org/10.1039/b9pp00102f

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