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Pure Appl. Chem., 2011, Vol. 83, No. 9, pp. 1721-1729

Published online 2011-08-03

A series of tetranuclear [2 × 2] grid complexes derived from an asymmetric ligand: Structural differences based on metal ion affinities

Takuya Shiga, Mao Noguchi, Takuto Matsumoto, Hiroki Sato, Hirotaka Tahira, Graham N. Newton and Hiroki Oshio*

Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai 1‑1-1, Tsukuba 305-8571, Japan

Abstract: A series of tetranuclear grid-type complexes were prepared by the reaction of the asymmetric multidentate ligand HL (HL = 2-[3-(2-hydroxyphenyl)-1H-pyrazol-5-yl]-6-pyridine carboxylic acid ethylester) with different metal sources. The tetranuclear copper complex, [Cu4(L1)4(NO3)4(H2O)4]·Et2O·2MeOH (1, HL1 = 2-[3-(2-hydroxyphenyl)-1H-pyrazol-5-yl]-6-pyridine carboxylic acid methyl ester) consists of four ligands, four copper ions, four nitrate ions and four water molecules, forming a [2 × 2] grid structure, in which all four copper ions have the same coordination environment. On the other hand, the corresponding nickel and cobalt complexes, [M4(L2)4(H2O)4]·4MeOH·6H2O (M = Ni (2) and Co (3), (H2L2 = 6-[1,3-dioxo-3-(2-phenyl)propionyl]pyridine-2-carboxylic acid)), have a similar grid core structure to the copper complex with four metal ions, four ligand molecules, and four water molecules, however, in these clusters there are two kinds of coordination site for the metal ions. Temperature-dependent magnetic susceptibility measurements for all complexes demonstrated that antiferromagnetic interactions between the metal ions were in operation. The magnetic susceptibility data of the copper and nickel complexes were analyzed using a tetranuclear model based on H = –2J(S1S2+S2S3+S3S4+S4S1) to give best-fit parameters of g = 2.11(1), J = –1.39(3) cm–1 and g = 2.19(1), J = –0.44(2) cm–1, respectively.