Supramolecular Heteropentamers As Building Blocks for Metal Organic Materials: Synthesis and Characterization of 1D and 2D 2-Fold Interpenetrated Frameworks

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• 作者：Jian-Jun Zhang ; Cynthia S. Day ; Mark D. Harvey ; Gordon T. Yee ; Abdessadek Lachgar
• 刊名：Crystal Growth & Design
• 出版年：2009
• 出版时间：February 4, 2009
• 年：2009
• 卷：9
• 期：2
• 页码：1020-1027
• 全文大小：386K
• 年卷期：v.9,no.2(February 4, 2009)
• ISSN：1528-7505

文摘

Reactions between (Me₄N)₄[Nb₆Cl₁₂(CN)₆], [Mn(ACEN)Cl] (ACEN^2- = bis(acetylacetonato)ethylenediamine), and dpyo (dpyo = 4,4′-dipyridyl-N,N′-dioxide) in different ratios led to the crystallization of two cluster-based metal-organic materials (CMOMs): {[Mn(ACEN)]₂[Mn(ACEN)(MeOH)]₂(Nb₆Cl₁₂(CN)₆)(dpyo)}·2MeCN (1) and {[Mn(ACEN)]₄(Nb₆Cl₁₂(CN)₆)(dpyo)₂}·MeCN·2MeOH·3.5H₂O (2). Their crystal structures were determined by single-crystal X-ray diffraction. Both materials are built of neutral heteropentamers {[Mn(ACEN)]₄[Nb₆Cl₁₂(CN)₆]} in which the edge-bridged hexacyano octahedral metal cluster [Nb₆Cl₁₂(CN)₆]^4- is functionalized by four [Mn(III)(ACEN)]⁺ complexes. The supramolecular assemblies are connected to each other by the ditopic ligand, dpyo. In 1, each heteropentamer is trans-bridged by two dpyo linkers to give a neutral chain. Hydrogen bonds between nonbridging cyanides and coordinated methanol ligands further connect the chains into layers which are separated by solvent molecules. In 2 each heteropentamer is trans-bridged by four dpyo linkers while each dpyo is cis-bridged by two heteropentamers to give a 4,4′-net with edge length of 25 Å. The 4,4′-nets are further interwoven into a 2-fold (2D → 2D) parallel interpenetrating layered structure. Magnetic properties and thermal stability of 1 and 2 are presented.