Three organic–inorganic hybrid copper–lanthanide heterometallic germanotungstates, {[Cu(en)2(H2O)] [Cu3Eu(en)3(OH)3(H2O)2](α-GeW11O39)}2·11H2O (1), {[Cu(en)2(H2O)][Cu3Tb(en)3(OH)3(H2O)2](α-GeW11O39)}2·11H2O (2) and {[Cu(en)2(H2O)][Cu3Dy(en)3(OH)3(H2O)2](α-GeW11O39)}2·10H2O (3) and three polyoxometalate hybrids built by lanthanide-containing germanotungstates and copper–ethylendiamine complexes, Na2H6[Cu(en)2(H2O)]8{Cu(en)2[La(α-GeW11O39)2]2}·18H2O (4), K4H2[Cu(en)2(H2O)2]5[Cu(en)2(H2O)]2[Cu(en)2]2{Cu(en)2[Pr(α-GeW11O39)2]2}·16H2O (5) and KNa2H7[enH2]3[Cu(en)2(H2O)]2[Cu(en)2]2{Cu(en)2[Er(α-GeW11O39)2]2}·15H2O (6) (en = ethylenediamine) have been hydrothermally synthesized and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP–AES) analyses, IR spectra, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. 1–3 are essentially isomorphous and their main skeletons display the interesting dimeric motif {[Cu3Ln(en)3(OH)3(H2O)2](α-GeW11O39)}24−, which is constructed from two {Cu3LnO4} cubane anchored monovacant [α-GeW11O39]8− fragments through two W–O–Ln–O–W linkers. The primary backbones of 4–6 exhibit the tetrameric architecture {Cu(en)2[Ln(α-GeW11O39)2]2}24− built by two 1
:2-type [Ln(α-GeW11O39)2]13− moieties and one [Cu(en)2]2+ bridge, albeit they are not isostructural. To our knowledge, 1–6 are rare polyoxometalate derivatives consisting of copper–lanthanide heterometallic/lanthanide germanotungstate fragments. 1 exhibits antiferromagnetic coupling interactions within the {Cu3EuO4} cubane units, while 2 and 3 display dominant ferromagnetic interactions between the TbIII/DyIII and CuII cations. The room-temperature solid-state photoluminescence properties of 1–3 have been investigated.
Dalton Transactions
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