Structural Studies of a Series of Organic Non-Linear Optical Materials

Abstract

The crystal structures of {4-[bis(diethylamino)methylium]phenyl}dicyanomethanide (I), {4-[cyano(4-methylpiperidyl)methylium]phenyl } dicyanomethanide (II), {4-[cyano(1-pyrrolidinyl)methylium]phenyl}dicyanomethanide (IV) and (Z)-{4-[1,3-dicyano-3-(diethylamino)-2-propenylium]phenyl} dicyanomethanide have been determined by X-ray crystallography. Together with (Z)-{4-[1-cyano-3-(diethylamino)-2-propenylium]phenyl}dicyanomethanide [(III): Cole, J. C., Howard, J. A. K., Cross, G. H. & Szablewski, M. (1995). Acta Cryst. C51, 715–718], these compounds exhibit varying degrees of quinoidal characteristics and yet have predominantly zwitterionic ground state character. The presence of high dipole moments in the crystal can thus be inferred and are substantiated by measurements of high solution-state dipole moments. Negative solvatochromism (hypsochromism on increasing solvent polarity) confirms the zwitterionic character in at least two of the series.