Three 3D organic–inorganic hybrid heterometallic polyoxotungstates assembled from 1:2-type [Ln(α-SiW11O39)2]13− silicotungstates and [Cu(dap)2]2+ linkers

Three organic–inorganic hybrid monolacunary Keggin silicotungstate-based 3d–4f heterometallic derivatives NaH[Cu(dap)2(H2O)][Cu(dap)2]4.5[Ln(α-SiW11O39)2]·7H2O (Ln = SmIII for 1, DyIII for 2, GdIII for 3) have been prepared by the hydrothermal reaction of Na10[A-α-SiW9O34]·18H2O, CuCl2·2H2O, LnCl3 and dap (dap = 1,2-diaminopropane) and characterized by elemental analyses, IR spectra and X-ray single-crystal diffraction. 1–3 display the novel 3D CuII–LnIII heterometallic frameworks with the scarce 5-connected (46·64) topology and their common features are that they all consist of 1:2-type [Ln(α-SiW11O39)2]13− subunits and [Cu(dap)2]2+ connectors. To the best of our knowledge, 1–3 represent the rare 3D organic–inorganic hybrid Keggin silicotungstate-based 3d–4f heterometallic derivatives. In addition, the photoluminescence properties of 1 and 2 have been investigated and the magnetic susceptibilities of 1–3 have been measured.

Graphical abstractThree organic–inorganic hybrid monolacunary Keggin silicotungstate 3d–4f heterometallic derivatives have been synthesized and characterized. The photoluminescence and magnetic properties have been investigated.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Organic–inorganic hybrid polyoxometalate-based 3d–4f heterometallic derivatives. ► 3D organic–inorganic hybrid 3d–4f heterometallic silicotungstates. ► The photoluminescence properties of the Sm and DyIII ions. ► The magnetism of Cu–Ln heterometallic silicotungstates.