AbstractThe reaction of the aryl‐oxide ligand H2L [H2L = N,N‐bis(3, 5‐dimethyl‐2‐hydroxybenzyl)‐N‐(2‐pyridylmethyl)amine] with CuSO4·5H2O, CuCl2·2H2O, CuBr2, CdCl2·2.5H2O, and Cd(OAc)2·2H2O, respectively, under hydrothermal conditions gave the complexes [Cu(H2L1)2]·SO4·3CH3OH (1), [Cu2(H2L2)2Cl4] (2), [Cu2(H2L2)2Br4] (3), [Cd2(HL)2Cl2] (4), and [Cd2(L)2(CH3COOH)2]·H2L (5), where H2L1 [H2L1 = 2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenol] and H2L2 [H2L2 = 2‐(2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenoxy)‐4, 6‐dimethylphenol] were derived from the solvothermal in situ metal/ligand reactions. These complexes were characterized by IR spectroscopy, elementary analysis, and X‐ray diffraction. A low‐temperature magnetic susceptibility measurement for the solid sample of 2 revealed antiferromagnetic interactions between two central copper(II) atoms. The emission property studies for complexes 4 and 5 indicated strong luminescence emission.