Interaction of manganese corroles with TCNQ and related acceptor molecules

Abstract

Manganese corroles with the Mn atom in the oxidation states +III and +IV have been probed as donor moieties for supramolecular stacked donor–acceptor complexes with the typical acceptor units TCNQ (tetracyanoquinone), TCNP (tetracyanopyrazine), and TCNB (tetracyanobenzene). Four new compounds formed as single crystals from different co-crystallization attempts. In those cases where a Mn(III) corrole was used as the donor component, hydrolyzed and/or oxygenated compounds [(cor)Mn(TCNQ*)] and [(cor*)Mn(TCNP*)] were obtained as the exclusive products. With chloridomanganese(IV) corroles, sandwich-like 2:1 complexes [(cor)MnCl][Formula: see text][TCNQ] and [(cor)MnCl][Formula: see text][TCNB] form, with both components left intact. Crystallographic analyses reveal partial or complete charge transfer to unusual axial ligands and thus prove the high reactivity of Mn(III) corroles in the first two cases. For the sandwich arrangements, almost-unaltered geometric parameters of the Mn(IV) corroles are observed, pointing to negligible structural consequences for metal corroles when engaged in stacking interactions.