Lanthanide Triangles Sandwiched by Tetranuclear Copper Complexes Afford a Family of Hendecanuclear Heterometallic Complexes [LnIII3CuII8] (Ln = La鈥揕u): Synt

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• 作者：Olga Iasco ; Ghenadie Novitchi ; Erwann Jeanneau ; Dominique Luneau
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：August 5, 2013
• 年：2013
• 卷：52
• 期：15
• 页码：8723-8731
• 全文大小：469K
• 年卷期：v.52,no.15(August 5, 2013)
• ISSN：1520-510X

文摘

Reaction in ethanol of 3-hydroxymethylen-5-methylsalicylaldoxime (H₃L) with CuCl₂路2H₂O and LnCl₃路xH₂O [Ln = La (1), Ce (2), Pr (3), Nd (4), Eu (5), Gd (6), Tb (7), Dy (8), Er (9), Yb (10), Lu (11), Ho (12)] allowed the synthesis of a family of hendecanuclear heterometallic copper(II)鈥搇anthanide(III) clusters with general formula [Ln^III₃Cu^II₈(HL)₆(渭₄-O)₂Cl₆(H₂O)₈]Cl₃ (1鈥?b>12). According to the single-crystal X-ray diffraction investigation, the complexes are isomorphous and crystallize in the trigonal R32 group. The hendecanuclear cluster is formed by two tetrahedral 渭₄-oxo {Cu₄} clusters assembled by three lanthanide ions sandwiched in between. Along the family, the separation between the {Cu₄} moieties increases linearly from Lu to La in good correlation with ionic radius of the lanthanide ions. A comparative analysis of the magnetic data for the lanthanum (1) and lutetium (11) compounds shows the presence of ferromagnetic and antiferromagnetic interactions within the 渭₄-oxo {Cu₄} moieties. For the gadolinium (6) and terbium (7) compounds, the magnetic interactions between the lanthanide and the copper ions are found to be ferromagnetic. The dysprosium (8) compound exhibits single-molecule magnet behavior.