A new class of second-order non-linear optical material: stilbazolium benzimidazolate derived from alkylsulfonyl substituted stilbazole

Abstract

A novel stilbazolium benzimidazolate derivative,i.e. 2-(4-{2-[4-(octylsulfonyl)phenyl]ethenyl}pyridinio)benzimidazolate 4a, was prepared by the quaternization reaction of 4-{2-[4-(octylsulfonyl)phenyl]ethenyl}pyridine with 2-chlorobenzimidazole, followed by deprotonation with aqueous ammonia. Poly(methyl methacrylate) (PMMA) thin films containing 10 or 20 mass% of 4a were obtained by spin-coating from their THF solutions on an ordinary cover glass substrate. Second-harmonic generation (SHG) measurements of the obtained thin films were carried out by the Maker fringe method using a Q-switched Nd:YAG laser (1064 nm) as an exciting beam after corona-poling. A poled PMMA film containing 10 or 20 mass% of 4a exhibited a second-order non-linear optical (NLO) coefficient, d33 , of 7.6 or 11 pm V–1 , respectively, which was much larger than the d33 value of a PMMA thin film containing 10 mass% of 2-[4-(2-phenylethenyl)pyridinio]benzimidazolate 4c (d33 1.6 pm V–1) or 2-{4-[2-(4-octyloxyphenyl)ethenyl]pyridinio}benzimidazolate 4d (d33 0.51 pm V–1). There were no significant differences in linear absorption properties of PMMA films containing 4a, 4c or 4d. The introduction of an octylsulfonyl group at the 4′-position of the stilbazole moiety increases the second-order NLO coefficient.