Novel building units in the construction of materials of the oxomolybdate-organodiphosphonate/copper(II)-dipodal-organonitrogen ligand system: Structural influences of dipodal ligand tether length and flexibility

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• 作者：Mark Bartholomä ; ¹ ; Hoi Chueng ; Steven Pellizzeri ; Kenneth Ellis-Guardiola ; Stephanie Jones ; Jon Zubieta ; ^{jazubiet@syr.edu}
• 关键词：Bimetallic oxide ; Copper&ndash ; molybdophosphonate materials ; Organic&ndash ; inorganic hybrid materials ; Pentamolybdate clusters ; Hexamolybdate clusters
• 刊名：Inorganica Chimica Acta
• 出版年：2012
• 期刊代码：40_00201693
• 类别：ch
• 出版时间：1 July, 2012
• 卷：389
• 期：Complete
• 页码：90-98
• 文件大小：1502 K

摘要

The hydrothermal reactions of copper(II) acetate, MoO₃, 1,4-butylenediphosphonic acid and a ligand of the N,N,N鈥?N鈥?tetrakis(pyridine-2-ylmethyl)alkyl-伪,蠅-diamine (Ln, where n is the number of methylene groups) in the presence of HF provided crystals of [{Cu₂(L7)(H₂O)₂}Mo₅O₁₅{O₃P(CH₂)₄PO₃}]路2H₂O (1路2H₂O) and [{Cu₂(L5)}Mo₆O₁₈(H₂O){O₃P(CH₂)₄PO₃}]路14H₂O (2路14H₂O). Compound 1 contains the common pentanuclear cluster building block {Mo₅O₁₅(O₃PR)₂}^{4鈭?/sup>, extending into one-dimensional chains through the alkyl tethers of the diphosphonate ligand. Each pentanuclear subunit bonds to four copper(II) sites of the {Cu₂(L7)(H₂O₂)}4+ subunits that serve to link each chain to five adjacent chains to propagate the structure in three dimensions. The Cu/Mo/P/O inorganic substructure which arises from this juxtaposition of building motifs is a one-dimensional {Cu₂Mo₅O₁₅(O₃P鈭?₂} unit consisting of clusters linked through Cu(II) sites. The alkyl arms of the diphosphonate and nitrogen ligands radiate outward to link to adjacent chains and propagate the structure in three-dimensions. In contrast, compound 2 exhibits a hexanuclear building unit {Mo₆O₁₈(H₂O)(O₃P鈭?₂}4鈭?/sup>, which again extends into a chain through the tethering diphosphonate ligands. Each cluster bonds to four Cu(II) centers to generate one-dimensional inorganic substructures of the type {Cu₂Mo₆O₁₈(H₂O)(O₃P鈭?₂}_n. In contrast to 1, the {Cu₂(L5)}4+ subunits of 2 associate with a single chain, rather than radiating outward to link to adjacent chains. Consequently, the three-dimensional expansion is effected through the diphosphonate tethers.}