One-Dimensional Coordination Polymers from Hexanuclear Manganese Carboxylate Clusters Featuring a {MnII4MnIII2(μ4-O)2} Core and S

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• 作者：Iurii L. Malaestean ; Victor Ch. Kravtsov ; Manfred Speldrich ; Galina Dulcevscaia ; Yurii A. Simonov ; Janusz Lipkowski ; Arkady Ellern ; Svetlana G. Baca ; Paul Kgerler
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：September 6, 2010
• 年：2010
• 卷：49
• 期：17
• 页码：7764-7772
• 全文大小：1163K
• 年卷期：v.49,no.17(September 6, 2010)
• ISSN：1520-510X

文摘

The bridging of hexanuclear mixed-valent carboxylate coordination clusters of the type [Mn₆O₂(O₂CR)₁₀] (R = CMe₃; CHMe₂) featuring a {Mn^II₄Mn^III₂(μ₄-O)₂} core by geometrically rigid as well as flexible spacer ligands such as pyrazine (pyz), nicotinamide (na), or 1,2-bis(4-pyridyl)ethane (bpe) results exclusively in one-dimensional (1D) coordination polymers. The formation of {[Mn₆O₂(O₂CCMe₃)₁₀(Me₃CCO₂H)(EtOH)(na)]·EtOH·H₂O}_n (1), {[Mn₆O₂(O₂CCHMe₂)₁₀(pyz)₃]·H₂O}_n (2), and {[Mn₆O₂(O₂CCHMe₂)₁₀(Me₂CHCO₂H)(EtOH)(bpe)]·Me₂CHCO₂H}_n (3) illustrates a surprising preference of the interlinked {Mn₆} units toward 1D coordination chains. In the solid-state, the observed chain propagation axes are either colinear (1 and 3) or perpendicular (2), whereby crystal packing is further influenced by solvent molecules. Magnetic properties of these network compounds can be rationalized based on that the magnetism of discrete [Mn₆O₂(O₂CR)₁₀]-type coordination clusters with all-antiferromagnetic intramolecular exchange and weak antiferromagnetic intercluster coupling in 1, 2, and 3 follows the expected exchange coupling strength of the employed spacer linkers.