Hybrid organic-inorganic 1D and 2D frameworks with epsilon-Keggin polyoxomolybdates as building blocks

Anne Dolbecq; Pierre Mialane; Laurent Lisnars; Jérôme Marrot; Francis Sécheresse

doi:10.1002/chem.200204670

Hybrid organic-inorganic 1D and 2D frameworks with epsilon-Keggin polyoxomolybdates as building blocks

Chemistry. 2003 Jun 16;9(12):2914-20. doi: 10.1002/chem.200204670.

Authors

Anne Dolbecq¹, Pierre Mialane, Laurent Lisnars, Jérôme Marrot, Francis Sécheresse

Affiliation

¹ Institut Lavoisier, IREM, UMR 8637, Université de Versailles Saint-Quentin, France. [email protected]

PMID: 12868423
DOI: 10.1002/chem.200204670

Abstract

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.