Two coordination polymers (CPs) [Cu2(L1)(µ3-OH)(H2O)]n (1) and {[Zn4(L)2(4,4′-bipy)3]•4H2O}n (2) were synthesized under solvothermal conditions. It is unexpectedly found the transformation of aryl−Br to aryl−Cl (Br-Cl exchange) in the formation of...

Two coordination polymers (CPs), namely, [Mn3(L)2(4,4′-bipy)2(H2O)2] n (1) and [Ni(L1)(1,4-bib)(H2O)] n (2) (H3L = 5-(3-bromo-4-carboxyphenoxy)isophthalic acid, H2L1 = 5-(3-hydroxyphenoxy)isophthalic acid, 4,4′-bpy = 4,4′-bipyridine, and 1,4-bib = 1,4-bis(1H-imidazol-1-yl)benzene), were synthesized under hydrothermal conditions. Most notably, with the help of the bromine atom-inducing effect, ligand transformation was observed in the structure of complex 2, which was scrutinized thoroughly by single crystal X-ray crystallography and X-ray photoelectron spectroscopy (XPS). Strikingly, Ni(II) ions were utilized as both coordinated atoms and as a catalyst for in situ Br–OH exchange of H3L in the process, as a result of which the product would have preferred to form a one-dimensional chain. The same reaction cannot happen in 1, leading to form a two-dimensional structure. Moreover, Ni(II)-catalyzed and magnetic exchange mechanisms were well interpreted using density functional theory (DFT) calculations. Finally, complexes 1–2 show three-dimensional (3D) supramolecular structures because of intermolecular weak interactions (C–Br···π, C–H···π, C–H···O, and π···π stacking) and exhibit utterly different antiferrimagnetic coupling interactions.