Two Organic-Inorganic Hybrids Assembled by Carboxylate-Bridging Lanthanide-Substituted Polyoxometalate Dimers with Copper-ethylendiamine Cations.

Two new organic-inorganic hybrid carboxylate-bridging copper-lanthanide heterometallic polyoxotungstates K[Cu(en)(HO)]{[Cu(en)][Ce(GeWO)(HO)](CO)}·11HO ( 1) and K [Cu(en)(HO)]{[Cu(en)(HO)][Tb(PWO)(CHCOO)(HO)]}·15HO ( 2) (en = 1,2-ethylenediamine) have been prepared under hydrothermal conditions and characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), thermogravimetric (TG) analyses and X-ray single-crystal diffraction. X-ray structural analyses reveal that 1 exhibits the 1D zigzag chain architecture formed by dimeric oxalate-bridging {[Cu(en)][Ce(GeWO)(HO)](CO)} units and [Cu(en)] linkers whereas 2 displays a typical hybrid acetate-bridging dimeric structure [(α-PWO)Tb(HO)(η,μ-1,1)-CHCOO] modified by [Cu(en)(HO)] fragments. Notably, both contain 2:2-type carboxylate-bridging monolanthanide-substituted Keggin-type dimeric moieties and two types of organic ligands. 1 represents the rare 1D Cu-Ln heterometallic germanotungstate containing mixed ligands of en and oxalate whereas 2 represents the rare dimeric organic-inorganic hybrid Keggin-type phosphotungstate containing both Cu-Ln heterometals and mixed ligands of en and acetate. Graphical Abstract: Two new organic-inorganic hybrid copper-lanthanide heterometallic polyoxotungstates containing mixed organic ligands of en and carboxylate were successfully separated under hydrothermal conditions. 1 exhibits the 1D zigzag chain architecture formed by dimeric oxalate-bridging {[Cu(en)][Ce(GeWO)(HO)](CO)} units by [Cu(en)] linkers, whereas 2 displays a typical hybrid acetate-bridging dimeric structure [(α-PWO)Tb(HO)(η,μ-1,1)-CHCOO] modified by [Cu(en)(HO)] fragments.[Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]