Assembly of tetra-nuclear YbIII-containing selenotungstate clusters: synthesis, structures, and magnetic properties

Abstract

Two tetra-nuclear Yb^III-incorporated selenotungstate clusters, Keggin (C₂H₈N)₆Na₁₄[Yb₄Se₆W₄₄O₁₆₀(H₂O)₁₂]·40H₂O (1) and Wells–Dawson (C₂H₈N)₄Na₁₄[Yb₄Se₆W₄₅O₁₅₉(OH)₆(H₂O)₁₁]·38H₂O (2), have been isolated through a pH-controlled assembly, which exhibit the first Yb^III-containing polyoxotungstates with selenium heteroatoms. Their assemblies rely on the structure-directing effects of SeO₃²⁻ anion templates to give rise to available Se-containing Keggin-/Wells–Dawson-type motifs. Both compounds were characterized by single-crystal X-ray diffraction, IR spectroscopy, power X-ray diffraction (XRD), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) as well as electrospray ionization mass spectrometry (ESI-MS). Furthermore, systematic magnetic studies revealed that 1 exhibits field-induced single-molecule magnetic behavior with a pre-exponential factor of τ₀ = 6.60(7) × 10⁻⁸ s and a relaxation energy barrier of ΔE/k_B = 39.44(2) K, while 2 only displays antiferromagnetic interactions between the ytterbium centers.