Self-Assembly of Nanoscale Lanthanoid-Containing Selenotungstates: Synthesis, Structures, and Magnetic Studies

The reaction of mid-lanthanide (Ln) ions with the preformed {Se₆W₃₉} precursor under reasonably acidic aqueous conditions in the presence of organic amine cations results in an unprecedented nanoscale lanthanide-functionalized polyoxotungstate family, which are rare examples of mid-lanthanide-containing selenotungstates. (C₄H₁₀NO)₉Na₃[Dy₃Se_3.5W₃₀O_107.5(H₂O)₁₀]·22H₂O (1) and (NH₄)₃(C₂H₈N)Na₂[Dy₄Se₆W₃₈O₁₃₂(H₂O)₂₆(OH)₆]·18H₂O (2) reveal a trimeric Keggin assembly and a cyclic {Se₆W₃₈}-based chain, respectively, whereas (NH₄)₄Na₈[Gd₄Se₆W₄₈O₁₆₆(H₂O)₂₀(OH)₄]·21H₂O (3) and (NH₄)₉(C₂H₈N)₄Na₅[Ln₆Se₆W₅₈O₂₀₂(H₂O)₂₀(OH)₄]·58H₂O (4; Ln = Gd, Tb, or Dy) are a few examples of polyoxometalates consisting of both classical Keggin and Wells-Dawson building blocks, and (NH₄)₄(C₂H₈N)₅Na₁₃[Ln₄Se₈W₅₆O₁₉₆(H₂O)(OH)₁₀]·40H₂O (5; Ln = Gd, Tb, or Dy; x = 12 for Gd and Tb and 10 for Dy) features the largest "pure" Wells-Dawson selenotungstate {Se₈W₅₆} bearing a length of 3.73 nm. A library of Se-templated species involving the first reported Keggin {α-SeW₈} and Wells-Dawson {α-Se₂W₁₆} building blocks as well as some decisive assembly factors during the synthesis is responsible for these architectures. All of the compounds were structurally characterized in the solid and solution by single-crystal X-ray diffraction, IR, thermogravimetric-differential thermal analysis, and electrospray ionization mass spectrometry. Magnetic properties indicate that 1 and 4-Dy show probable single-molecule-magnet behavior with obvious frequency dependence, whereas 3 and 4-Gd present the antiferromagnetic interactions between the Gd^III centers.