Structure-directed functional properties of symmetrical and unsymmetrical Br-substituted Schiff-bases

This study deals with the investigation of two low molecular weight Schiff base compounds with bromine end groups, differing only by the presence or absence of one methyl group, with the aim of better understanding the solution and the solid state optical, electrochemical and thermic properties generated by the small structural features. The compounds were structurally characterized by 1H NMR, 13C NMR and FTIR spectroscopies, single-crystal X-ray diffraction and gas chromatography analysis. Their thermal behavior was evidenced by polarized light microscopy and differential scanning calorimetry. The single crystal structure of the compounds reveals the versatility of bromine substituents which can adopt an attractive or repulsive electron effect, driven by the structural environment. A comparison of the structures shows that the introduction of a methyl unit as a bulky group hinders completely the π–π stacking interaction within the structural rows, inducing larger intermolecular distances resulting in quite different functional physical and chemical properties.