Dolbecq Anne, Mialane Pierre, Lisnars Laurent, Marrot Jérôme, Sécheresse Francis
Institut Lavoisier, IREM, UMR 8637, Université de Versailles Saint-Quentin, France.
Chemistry. 2003 Jun 16;9(12):2914-20. doi: 10.1002/chem.200204670.
Organic-inorganic hybrid materials based on polyoxometalate building blocks with capping La3+ ions and bidentate oxygenated ligands have been obtained by reaction at room temperature of the [epsilon-PMo12O36(OH)4[La(H2O)4]]5+ polyoxocation with glutarate (C5H6O(2)(2-)) and squarate (C4O(4)(2-)) organic ligands. [epsilon-PMo12O37(OH)3[La(H2O)4(C5H6O4)0.5]4].21 H2O (1) and [epsilon-PMo12O39(OH)[La(H2O)6]2-[La(H2O)5(C4O4)0.5]2].17 H2O (2) form unprecedented 1D chains built from alternating polyoxocations and organic ligands connected through LaO links. The structures of these materials are compared to the 2D hybrid organic-inorganic framework [NC4H12]2-[Mo22O52(OH)18[La(H2O)4]2[La(CH3CO2)2]4].8H2O (3) isolated from the hydrothermal reaction of elemental precursors (MoO(4)(2-), Mo, La3+) in acetate buffer. Compound 3 is built from previously undescribed polyoxometalate units with twenty-two MoV centers capped by six La3+ ions, four of which are bridged by acetate ligands.
基于具有封端La³⁺离子和双齿含氧配体的多金属氧酸盐构建块的有机-无机杂化材料，是通过[ε-PMo₁₂O₃₆(OH)₄[La(H₂O)₄]]⁵⁺聚氧阳离子与戊二酸（C₅H₆O₂²⁻）和方酸（C₄O₄²⁻）有机配体在室温下反应得到的。[ε-PMo₁₂O₃₇(OH)₃[La(H₂O)₄(C₅H₆O₄)₀.₅]₄].21H₂O（1）和[ε-PMo₁₂O₃₉(OH)[La(H₂O)₆]₂-[La(H₂O)₅(C₄O₄)₀.₅]₂].17H₂O（2）形成了前所未有的一维链，该链由交替的聚氧阳离子和通过LaO键连接的有机配体构成。将这些材料的结构与从元素前驱体（MoO₄²⁻、Mo、La³⁺）在醋酸盐缓冲液中的水热反应中分离出的二维有机-无机杂化框架[NC₄H₁₂]₂-[Mo₂₂O₅₂(OH)₁₈[La(H₂O)₄]₂[La(CH₃CO₂)₂]₄].8H₂O（3）进行了比较。化合物3由以前未描述的多金属氧酸盐单元构成，该单元有22个MoV中心，由6个La³⁺离子封端，其中4个由醋酸盐配体桥连。
