Syntheses, structures and properties of dimeric rare earth derivatives based on monovacant Keggin-type polyoxotungstates

Three lanthanide (Ln) substituted polyoxometalates [{(α-PW11O39H2)Ln(H2O)(η2,μ-1,1)-CH3COO}2]10− (Ln = Dy(III) for 1, Y(III) for 2, Lu(III) for 3) have been synthesized successfully in moderate aqueous solution and characterized by elemental analyses, IR spectra, UV spectroscopy, thermogravimetric analyses, fluorescence spectra, X-ray powder diffraction (XRPD) and single-crystal X-ray diffraction. The structure analyses reveal that 1–3 are isostructural and constructed by two mono-lanthanide substituted units [(α-PW11O39H2)Ln(H2O)(η2,μ-1,1)-CH3COO]5−, which are bridged by two (η2,μ-1,1)-acetato ligands. The solid-state photoluminescence properties of 1–3 were studied and the results indicate that only 1 demonstrates yellow luminescence. Magnetic measurements reveal that 1 shows spin–orbital coupling interactions and weak antiferromagnetic exchange interactions.

Graphical abstractThree isostructural lanthanide (Ln) substituted polyoxometalates [{(α-PW11O39H2)Ln(H2O)(η2,μ-1,1)-CH3COO}2]10− (Ln = Dy(III) for 1, Y(III) for 2, Lu(III) for 3) have been obtained, which are constructed by two mono-lanthanide substituted units [(α-PW11O39H2)Ln(H2O)(η2,μ-1,1)-CH3COO]5− bridged by two (η2,μ-1,1)-acetato ligands.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Dy, Y and Lu substituted the monovacant polyoxometalates. ► Two mono-lanthanide substituted units construct the dimer. ► Bridged by two (η2,μ-1,1)-acetato ligands. ► Dy demonstrates yellow luminescence. ► Lu shows spin–orbital coupling interactions and weak antiferromagnetic exchange interactions.