title: Excited-state intramolecular proton transfer on 2-(2'-hydroxy-4'-R-phenyl)benzothiazole nanoparticles and fluorescence wavelength depending on substituent and temperature.
abstract: The fluorescence emission properties of 2-(2'-hydroxy-4'-R-phenyl)benzothiazole (HBT-R) nanoparticles with different substituents (R = -COOH, -H, -CH(3), -OH, and -OCH(3)) 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 degrees C. A mechanism of a temperature-dependent equilibrium between the nanoparticles and the solvated enols is proposed for the emission color change.
authors.affiliation: BT Convergence Technology Research Department, ETRI, Daejeon, 305-700, Korea. josephinkim@etri.re.kr
authors.forename: Yong Hee
authors.initials: YH
authors.lastname: Kim
authors.forename: Soo-Gyun
authors.initials: SG
authors.lastname: Roh
authors.forename: Sang-Don
authors.initials: SD
authors.lastname: Jung
authors.forename: Myung-Ae
authors.initials: MA
authors.lastname: Chung
authors.forename: Hwan Kyu
authors.initials: HK
authors.lastname: Kim
authors.forename: Dae Won
authors.initials: DW
authors.lastname: Cho