Synthesis, Structural, Magnetic and Computational Studies of a One-Dimensional Ferromagnetic Cu(II) Chain Assembled from a New Schiff Base Ligand
A new asymmetrically substituted ONOO Schiff base ligand N-(2′-hydroxy-1′-naphthylidene)-3-amino-2-naphthoic acid (nancH2) was prepared from the condensation of 2–hydroxy–1–naphthaldehyde and 3–amino–2–naphthoic acid. nancH2 reacts with Cu2(O2CMe)4·2H2O in the presence of Gd(O2CMe)3·6H2O to afford a uniform one-dimensional homometallic chain, [CuII(nanc)]n (1). The structure of 1 was elucidated via single crystal X-ray diffraction studies, which revealed that the Cu(II) ions adopt distorted square planar geometries and are coordinated in a tridentate manner by an [ONO] donor set from one nanc2− ligand and an O− of a bridging carboxylate group from a second ligand. The bridging carboxylato group of the nanc2− ligand adopts a syn, anti-η1:η1:μ conformation linking neighboring Cu(II) ions, forming a 1D chain. The magnetic susceptibility of 1 follows Curie–Weiss law in the range 45–300 K (C = 0.474(1) emu K mol-1, θ = +7.9(3) K), consistent with ferromagnetic interactions between S = ½ Cu(II) ions with g = 2.248. Subsequently, the data fit well to the 1D quantum Heisenberg ferromagnetic (QHFM) chain model with g = 2.271, and J = +12.3 K. DFT calculations, implementing the broken symmetry approach, were also carried out on a model dimeric unit extracted from the polymeric chain structure. The calculated exchange coupling via the carboxylate bridge (J = +13.8 K) is consistent with the observed ferromagnetic exchange between neighbouring Cu(II) centres. © 2023 by the authors.
This article belongs to the Special Issue Coordination Chemistry: Current Developments and Future Perspectives — a Themed Issue in Honor of Professor Spyros P. Perlepes on the Occasion of His 70th Birthday)
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Worrell, Anne; Delle Monache, Gabriele; Turnbull, Mark M.; Rawson, Jeremy M.; Stamatatos, Theocharis C.; and Pilkington, Melanie, "Synthesis, Structural, Magnetic and Computational Studies of a One-Dimensional Ferromagnetic Cu(II) Chain Assembled from a New Schiff Base Ligand" (2023). Chemistry. 9.
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