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(L1)]2·CH2Cl2 and [{Co(L2)(EtOH)}2Co(H2O)]·EtOH {H2L1 = 4,6‐dichloro‐6′‐methyoxy‐2,2′‐[1,1′‐(ethylenedioxydinitrilo)dimethylidyne]diphenol and H3L2 = 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 CuII complex, the CuII atom is four‐coordinate, with a N2O2 coordination sphere, and has a slightly distorted square‐planar arrangement. Interestingly, the obtained trinuclear CoII complex is different from the common reported 2:3 (L:CoII) salamo‐type CoII complexes. Infinite 2D layer supramolecular structures are formed via abundant intermolecular hydrogen bonding and π···π stacking interactions in the CuII and CoII complexes.