Seven organic–inorganic hybrid lanthanide dimolybdates [Ln(H2O)6Mo2O6(Hpydc)(pydc)]·nH2O (n = 0: Ln = LaIII (1), CeIII (2), PrIII (3), NdIII (4), SmIII (5); n = 0.5: Ln = EuIII (6)), and Na0.5H0.5[Er(H2O)5Mo2O6(pydc)2]·3H2O (7) (H2pydc = pyridine-2,5-dicarboxylic acid) have been hydrothermally prepared and further characterized by elemental analyses, X-ray powder diffraction (XRPD), IR spectra, thermogravimetric (TG) analyses, and single-crystal X-ray diffraction. The common feature of 1–7 is that they all consist of LnIII cations and MoIV centers connected by oxygen atoms and H2pydc ligands. 1–6 show unprecedented 3D 8-connected networks with the Schläfli symbol of (34·417·54·63), while 7 exhibits the 2D 4-connected (45·6) structure. Furthermore, the luminescence properties of 5 and 6 are derived from the combination of Ln cations and H2pydc ligands, whereas 1–4 and 7 are attributable to H2pydc ligands.
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