Construction of Mononuclear Copper(II) and Trinuclear Cobalt(II) Complexes Based on Asymmetric Salamo‐Type Ligands

Mononuclear copper(II) and trinuclear cobalt(II) complexes, namely [Cu(L 1 )] 2 · CH 2 Cl 2 and [{Co(L 2 )(EtOH)} 2 Co(H 2 O)] · EtOH {H 2 L 1 = 4,6‐dichloro‐6′‐methyoxy‐2,2′‐[1,1′‐(ethylenedioxydinitrilo)dimethylidyne]diphenol and H 3 L 2 = 6‐ethyoxy‐6′‐hydroxy‐2,2′‐[1,1′‐(ethylenedioxydinitrilo)dimethylidyne]diphenol}, were synthesized and characterized by elemental analyses, IR and UV/Vis spectroscopy, and single‐crystal X‐ray diffraction. In the Cu II complex, the Cu II atom is four‐coordinate, with a N 2 O 2 coordination sphere, and has a slightly distorted square‐planar arrangement. Interestingly, the obtained trinuclear Co II complex is different from the common reported 2:3 (L:Co II ) salamo‐type Co II complexes. Infinite 2D layer supramolecular structures are formed via abundant intermolecular hydrogen bonding and π ··· π stacking interactions in the Cu II and Co II complexes.