Tuning Dimensions of Complexes through Selective In Situ Reaction, Mechanistic Insights into Ni(II)-Catalyzed Br–OH Exchange, Magnetic Properties, and Density Functional Theory Studies

• Published in: Inorganic chemistry Vol. 61; no. 49; pp. 20159 - 20168
• Main Authors: Si, Chang-Dai, Zhang, Jian-Bin, Pan, Feng-Feng, Yan, Xu, Wang, Peng, Xue, Dong-Qian, Li, Xiu-Juan, Liu, Jia-Cheng, Yuan, Kun
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 12.12.2022
• Subjects: Density Functional Theory; Magnetic Phenomena; Models, Molecular; Phthalic Acids
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.2c03643

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.