Nitrito-κN ligand in pentacyanidocobaltate(III) linkers as a polarity inducer in heterometallic frameworks incorporating lanthanide(III) molecular nanomagnets

Abstract

We report a symmetry-breaking effect in the family of coordination polymers, {[Ln^III(4,4'-bipyridine-N,N'-dioxide)₂(OH₂)₄][Co^III(CN)₅(NO₂)]}•2H₂O (Ln = La-Nd, Sm), induced by uncommon pentacyanidocobaltate linkers bearing nitrito-κN ligands. Resulting structural polarity leads to a strong and tunable non-linear optical response, while incorporated lanthanide complexes exhibit slow relaxation of magnetization and near-infrared photoluminescence.