title: Organic styryl dye nanoparticles: synthesis and unique spectroscopic properties.
abstract: We report the synthesis and unique spectroscopic properties of organic styryl dye nanoparticles. Aqueous-phase ion association between a cationic styryl dye 2-(4-(dimethylamino)styryl)-1-ethylpyridinium (DASPE), possessing both electron donor and acceptor groups in its molecule, and tetraphenylborate (TPB) or tetrakis(4-fluorophenyl)borate (TFPB) anion, in the presence of poly(vinylpyrrolidone), produces the ion-based dye (DASPE) nanoparticles of approximately 30-100 nm in diameter. Absorption spectra of the DASPE nanoparticles show a large bathochromic shift in comparison with that of the dye monomer in water. Quantum chemical calculations demonstrate that ion-pair formation brings about a large internal rotation around a single bond in DASPE, and this internal twisting as well as local polarity of the counteranion have a strong influence on the red shift of the optical spectra. Furthermore, nanoparticle formation results in enhanced fluorescence of DASPE: more than a 20-fold enhancement in the fluorescence quantum yield as compared to that of the dye monomer in water, giving a new methodology for the synthesis of fluorescent organic nanoparticles. The observed fluorescence would come from an intramolecular charge-transfer (ICT) excited state stabilized by the matrix of TPB or TFPB, and the enhancement is due to both the high rotational resistance for the single bond in DASPE and the matrix polarity effect that can suppress the nonradiative processes.
authors.affiliation: Graduate School of Material Science, University of Hyogo, 3-2-1 Koto, Kamigori-cho, Ako-gun, Hyogo, 678-1297 Japan. yao@sci.u-hyogo.ac.jp
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Yao
authors.forename: Minami
authors.initials: M
authors.lastname: Yamashita
authors.forename: Keisaku
authors.initials: K
authors.lastname: Kimura