TY - JOUR
T1 - Preparation and crystal structures of new colorless 4-amino-1-methylpyridinium benzenesulfonate salts for second-order nonlinear optics
AU - Anwar,
AU - Okada, S.
AU - Oikawa, Hidetoshi
AU - Nakanishi, H.
PY - 2000/10/17
Y1 - 2000/10/17
N2 - A series of ionic 4-amino-1-methylpyridinium benzenesulfonate salts have been prepared by quaternization reaction of 4-aminopyridine with methyl benzenesulfonates having a substituent of hydroxy, methoxy, methyl, chloro, or bromo group at para position. The X-ray structure analysis has been performed for their single crystals which were obtained by slow evaporation of their methanol solutions. The salts were found to crystallize into noncentrosymmetric structures; triclinic space group P1 for the hydroxy derivative, monoclinic space group P21 for the methoxy and methyl derivatives, and monoclinic space group Cc for the chloro and bromo derivatives. By using the molecular structures and the molecular first hyperpolarizability (β) of the corresponding cation and anions, the components of second-harmonic tensor coefficient d of the crystals were evaluated by the oriented-gas model. The diagonal d components of the crystals were estimated to be as large as one-fourth of that of 2-methyl-4-nitroaniline (MNA) at 1064-nm laser wavelength irrespective of their very short absorption cutoff wavelength in the UV region. These colorless crystals could be a new series of prospective crystalline materials for second-order nonlinear optical applications using conventional diode lasers.
AB - A series of ionic 4-amino-1-methylpyridinium benzenesulfonate salts have been prepared by quaternization reaction of 4-aminopyridine with methyl benzenesulfonates having a substituent of hydroxy, methoxy, methyl, chloro, or bromo group at para position. The X-ray structure analysis has been performed for their single crystals which were obtained by slow evaporation of their methanol solutions. The salts were found to crystallize into noncentrosymmetric structures; triclinic space group P1 for the hydroxy derivative, monoclinic space group P21 for the methoxy and methyl derivatives, and monoclinic space group Cc for the chloro and bromo derivatives. By using the molecular structures and the molecular first hyperpolarizability (β) of the corresponding cation and anions, the components of second-harmonic tensor coefficient d of the crystals were evaluated by the oriented-gas model. The diagonal d components of the crystals were estimated to be as large as one-fourth of that of 2-methyl-4-nitroaniline (MNA) at 1064-nm laser wavelength irrespective of their very short absorption cutoff wavelength in the UV region. These colorless crystals could be a new series of prospective crystalline materials for second-order nonlinear optical applications using conventional diode lasers.
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U2 - 10.1021/cm990794k
DO - 10.1021/cm990794k
M3 - Article
AN - SCOPUS:0033803926
VL - 12
SP - 1162
EP - 1170
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 4
ER -