Tripyrrin-armed isosmaragdyrins: synthesis, heterodinuclear coordination, and protonation-triggered helical inversion

Oxidative ring closure of linear oligopyrroles is one of the synthetic approaches to novel porphyrinoids with dinuclear coordination sites and helical chirality. The spatial arrangement of the pyrrolic groups of octapyrrole ( P8 ) affected the position of the intramolecular oxidative coupling of the pyrrolic units; tripyrrin-armed isosmaragdyrin analogue ( 1 ) containing a β,β-linked bipyrrole moiety was synthesized regioselectively in a high yield by using FeCl 3 . Ni II -coordination at the armed tripyrrin site of 1 allowed the formation of diastereomeric helical twisted complexes ( 2A and 2B ) and succeeding Cu II -coordination at the macrocyclic core afforded heterodinuclear Ni II /Cu II -complexes ( 3A and 3B ). Each of them comprised a pair of separable enantiomers, exhibiting P - and M -helices, respectively. Notably, diastereomeric interconversion from 2A to 2B was quantitatively achieved as a consequence of helical transformation under acidic conditions. A tripyrrin-armed isosmaragdyrin containing a β,β-linked bipyrrole moiety has been synthesized from a linear octapyrrole, and the succeeding metallation afforded an enantiomer pair of mononuclear Ni II - and heterodinuclear Ni II /Cu II -complexes that exhibit P - and M -helices.