Tetracarboxylate Ligands as New Chelates Supporting Copper(II) Paddlewheel-Like Structures

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• 作者：Antoine Gomila ; Sylvain Duval ; C茅line Besnard ; Karl W. Kr盲mer ; Shi-Xia Liu ; Silvio Decurtins ; Alan F. Williams
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：March 3, 2014
• 年：2014
• 卷：53
• 期：5
• 页码：2683-2691
• 全文大小：454K
• 年卷期：v.53,no.5(March 3, 2014)
• ISSN：1520-510X

文摘

Two new ligands N,N,N鈥?N鈥?tetrakis(2-methylbenzoic acid)-1,4-diaminomethylbenzene, 5H₄, and N,N,N鈥?N鈥?tetrakis(2-methylbenzoic acid)-4,4鈥?diaminomethyldiphenyl, 6H₄, carrying four carboxylate groups suitable for bridging dinuclear centers have been prepared and their paddlewheel complexes with copper(II) prepared. The phenyl-bridged ligand 5H₄ gives a cyclic octanuclear species [(Cu₂)₄(5)₄], while the diphenyl-bridged ligand 6H₄ gives a lantern-like tetranuclear species [(Cu₂)₂(6)₂]; both were characterized by X-ray crystallography. If the amine functions of 5 are protonated, intramolecular hydrogen bonds position the four carboxylates in such a way as to allow formation of the unusual compound [Cu₄(5H₂)₂Cl]³⁺ in which a Cu₄ square centered by a chloro ligand is sandwiched between two (5H₂)^{2鈥?/sup> ligands. The magnetic properties of this compound have been studied and show antiferromagnetic coupling between adjacent coppers (J = 鈭?3.7 cm鈥?).}