The windmill, the dragon, and the frog: geometry control over the spectral, magnetic, and electrochemical properties of cobalt phthalocyanine regioisomers†

Abstract

For the first time, we have prepared non-aggregating phthalocyanine cobalt complexes as a set of resolved positional isomers. These compounds comprise a unique test bed for the structure–properties studies, as their optical and electrochemical properties are influenced by the planarity of the phthalocyanine macrocycle, which can be controlled by the positional isomerism of the bulky aromatic substituents at the α-phthalo sites. We support our conclusions with molecular modelling studies, which show a perfect match between the calculated and experimentally determined spectral/electrochemical values. We challenge a common perception that the NMR spectra of cobalt phthalocyanines cannot be measured due to the paramagnetic nature of Co(II). We suggest instead that the key factors affecting the NMR spectral resolution are molecular aggregation and π–π stacking. These interactions are suppressed by the bulky peripheral substituents on the cobalt phthalocyanines prepared, making these isomeric compounds an excellent tool for paramagnetic NMR studies.