Exercises in molecular gymnastics--bending, stretching and twisting porphyrins.

The functional versatility of tetrapyrroles as natural cofactors is related to their conformational flexibility where manipulation of the macrocycle conformation allows a fine-tuning of their physicochemical properties. This feature article gives a personal account of the synthesis and solid state structural characterization of highly substituted, non-planar porphyrins. Their conformational analysis identifies sterically strained tetrapyrroles as a versatile class of biomimetic compounds with tailor-made properties.