Self-Assembly Of Ln(Iii)-Containing Tungstotellurates(Vi): Correlation Of Structure And Photoluminescence

The generation of five types of Ln(III)-containing tungstotellurates(VI), dimeric (DMAH)(12)Na-2[H-10(WO2) {Ln-(H2O)(5)(TeW18O65)}(2)]center dot nH(2)O (abbreviated as{Ln(2)Te W-2(37)}; Ln = Eu, Gd, or Tb; DMAH = dimethylammonium), tetrameric- (DMAH)(21)Na-7[H-16{Ln(H2O)(5)(TeW18O64)}(4)]center dot nH(2)O (abbreviated as {Ln(4)Te(4)W(72)}, Ln = Eu or Gd), 2:2 dimeric (DMAH)(12)[H-6{Tb-(H2O)(3)(TeW17O61)}(2)]center dot 2SH(2)O (abbreviated as {Tb2Te2W34}), 1:1 monosubstituted (DMAH)(7)Na-2[H2Tb(H2O)(4)(TeW17O61)]center dot 21H(2)O (abbreviated & nbsp; as {TbTeW17}), and three-dimensional polymer(DMAH)(2)[HundefinedTb(H2O)(4){TeW6O24}]center dot 14H(2)O (abbreviated as{TbTeW6}(n)), provides insight into the rich condensation chemistry of lacunary and other Dawson-type polyoxometalates. The pH and the type of Ln(3+)undefined source both dictate which of these new complexes form. To our knowledge, {Ln(4)Te(4)W(72)} is the highest-nuclearity tungstotellurate to date, and {Tb2Te2W34} and {TbTeW17} contain the first lacunary {TeW17O61}. Electrospray ionization mass spectra analyses indicate that the Dawson-like building blocks, {TeW18O65} and {TeW17O61}, found in solid structures are also present in solution. The intense photoluminescence (characteristic green emission) of {TbTeW6}n, 100X greater than those of {Tb2Te2W37}, {Tb2Te2W34}, and {TbTeW17}, is explained by analysis of all 4 X-ray structures and multiple structure-intensity correlations.