Fluorescent and nonfluorescent crystals of N-(3,5-dihalogenosalicylidene)-2-methoxyaniline

Abstract

Crystals of N-(3,5-diXsalicylidene)-2-methoxyaniline (X = fluoro, chloro, bromo, and iodo) were prepared, and their structural and luminescence properties in the solid state were investigated. Only fluorescent orange crystals were obtained for N-(3,5-difluorosalicylidene)-2-methoxyaniline (1). Both fluorescent orange crystals (2a) and nonfluorescent red–orange crystals (2b) were obtained for N-(3,5-dichlorosalicylidene)-2-methoxyaniline. Slightly fluorescent orange crystals were obtained for N-(3,5-dibromosalicylidene)-2-methoxyaniline (3) and N-(3,5-diiodosalicylidene)-2-methoxyaniline (4). Fluorescence spectra of 1, 2a, 3, and 4 in the solid state show a fluorescence band at around 600 nm by excitation at 480 nm. The fluorescence intensities were in the order 1 > 2a > 3 > 4. X-ray crystal-structure analyses of 1, 2a, and 2b were obtained. The N-salicylideneaniline molecules in all of the crystals have planar structures. The molecules in both 1 and 2b take the enol form, while the molecules in 2a take the cis-keto form. The crystals 2a include water of crystallization, which is hydrogen bonded to the adjacent N-salicylideneaniline molecules. Molecules in fluorescent 2a are arranged in stacks along the a-axis to form a columnar structure in the crystals. In contrast, molecules in nonfluorescent 2b are strongly π–π stacked to form dimers in crystals. The orange crystals 2a were transformed to the red–orange crystals 2b by removal of water of crystallization upon heating at 70 °C.