Functionalized Adamantane Tectons Used in the Design of Mixed-Ligand Copper(II) 1,2,4-Triazolyl/Carboxylate Metal鈥揙rganic Frameworks

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• 作者：Ganna A. Senchyk ; Andrey B. Lysenko ; Harald Krautscheid ; Eduard B. Rusanov ; Alexander N. Chernega ; Karl W. Kr盲mer ; Shi-Xia Liu ; Silvio Decurtins ; Konstantin V. Domasevitch
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：January 18, 2013
• 年：2013
• 卷：52
• 期：2
• 页码：863-872
• 全文大小：711K
• 年卷期：v.52,no.2(January 18, 2013)
• ISSN：1520-510X

文摘

Bistriazoles, 1,3-bis(1,2,4-triazol-4-yl)propane (tr₂pr) and 1,3-bis(1,2,4-triazol-4-yl)adamantane (tr₂ad), were examined in combination with the rigid tetratopic 1,3,5,7-adamantanetetracarboxylic acid (H₄-adtc) platform for the construction of neutral heteroleptic copper(II) metal鈥搊rganic frameworks. Two coordination polymers, [{Cu₄(OH)₂(H₂O)₂}{Cu₄(OH)₂}(tr₂pr)₂(H-adtc)₄]路2H₂O (1) and [Cu₄(OH)₂(tr₂ad)₂(H-adtc)₂(H₂O)₂]路3H₂O (2), were synthesized and structurally characterized. In complexes 1 and 2, the N¹,N²-1,2,4-triazolyl (tr) and 渭₃-OH^{鈥?/sup> groups serve as complementary bridges between adjacent metal centers supporting the tetranuclear dihydroxo clusters. The structure of 1 represents a unique association of two different kinds of centrosymmetrical {Cu₄(OH)₂} units in a tight 3D framework, while in compound 2, another configuration type of acentric tetranuclear metal clusters is organized in a layered 3,6-hexagonal motif. In both cases, the {Cu₄(OH)₂} secondary building block and trideprotonated carboxylate H-adtc3鈥?/b> can be viewed as covalently bound six- and three-connected nodes that define the net topology. The tr ligands, showing 渭₃- or 渭₄-binding patterns, introduce additional integrating links between the neighboring {Cu₄(OH)₂} fragments. A variable-temperature magnetic susceptibility study of 2 demonstrates strong antiferromagnetic intracluster coupling (J₁ = 鈭?09 cm鈥? and J₂ = 鈭?1 cm鈥?), which combines for the bulk phase with a weak antiferromagnetic intercluster interaction (zj = 鈭?.5 cm鈥?).}