Structure–property relationships for 1,7-diphenoxy-perylene bisimides in solution and in the solid state

Abstract

To elucidate the impact of widely employed solubilizing phenoxy substituents on the structural and functional properties of perylene bisimide (PBI) dyes a series of 1,7-diphenoxy-substituted PBIs was prepared from 1,7-dibromo PBI which exhibit hydrogen, methyl, isopropyl or phenyl substituents at one or both ortho positions of the phenoxy substituents. Despite increasing sterical congestion high yields of 74–88% could be obtained for all twofold aromatic nucleophilic substitution reactions. The structural and optical properties in solution and in the solid state were investigated by ¹H NMR, UV-Vis absorption and fluorescence spectroscopy, single crystal X-ray analyses (four structures) as well as quantum chemical and force field calculations. For the latter we used an adapted force field which correctly reflects the rigidity of the PBI core. Our studies show that these dyes prefer to accommodate a slightly twisted molecular structure in solution that is supported by CH⋯O hydrogen bonds between the 1,7-oxygen and the 6,12-hydrogen substituents. Because of the rather shallow potential energy surface, however, the molecules may planarize in the crystalline state under the influence of packing forces as revealed by single crystal X-ray analyses for two derivatives bearing methyl or phenyl substituents at all phenoxy ortho-positions. Such substituents are also suited to enwrap the PBI π-scaffold and to prohibit PBI aggregation in the bulk state giving rise to defined vibronic progressions in the solid state UV-Vis absorption and emission spectra, and appreciable fluorescence quantum yields of up to 37%. In dichloromethane solution all of these 1,7-diphenoxy-substituted PBI dyes exhibit fluorescence quantum yields of 98–100% despite significant differences in the shape of the UV-Vis absorption band. The latter was explained in terms of rigidity because the molecules bearing four ortho-substituents at the phenoxy substituents were shown to prevail in much more fixed conformations compared to their more simple counterparts. Our findings underline that the conformational flexibility of bay-substituents can have an important impact on the functional properties of PBI dyes.