Physicochemical studies of molecular hyperpolarizability of imidazole derivatives

A series of substituted imidazoles have been synthesized in very good yield under solvent free condition by grinding 1,2-diketone, arylaldehyde, arylamine and ammonium acetate in the presence of molecular iodine as the catalyst. The short reaction time, good yield and easy workup make this protocol practically and economically attractive and the imidazoles are characterized by NMR spectra, X-ray, mass and CHN analysis. The push–pull character of series of imidazoles have been analyzed by the quotient of the occupations of the bonding (π) and anti-bonding (π*) orbitals of the central linking –NC–CC– unit. Excellent correlation of the push–pull parameter with the corresponding bond lengths dCN and dCC strongly recommend both the occupation quotients (π*/π) and the corresponding bond lengths are reasonable sensors for quantifying the push–pull character and for the molecular hyperpolarizability ß0 of these compounds. To support the experimental results, theoretical calculations (heat of formation, NLO, NBO and vibrational analysis) were also made. Within this context, reasonable conclusions concerning the steric hindrance in the chromospheres, push–pull character, hyperpolarizability of the imidazoles and their application as NLO materials will be drawn.

Graphical abstractConclusions concerning the steric hindrance in the chromospheres, push–pull character, hyperpolarizability of the imidazoles and their application as NLO materials will be drawn.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Presence of α twist in these imidazoles drops the fluorescence quantum yield. ► Dependence of β versus σπ*/π/2 shows polarity is important for its use as NLO material. ► Molecules of higher β values have larger dipole moments are used as NLO molecules.