Incorporating polyoxometalates and organic ligands to pursue 3d–4f heterometallic clusters: a series of {Cr4Ln4} clusters stabilized by phthalic acid and [SiW12O40]4−

Abstract

By introduction of trilacunary Keggin-type polyoxometalate to the hydrothermal reaction system of Cr³⁺, Ln³⁺ and phthalic acid, a series of novel {Cr₄Ln₄} heterometallic clusters with the formula Cs₂[Cr₄Ln₄(μ₄-O)₄(μ₃-O)₄(C₈H₄O₄)₄(H₂O)₁₂](H₃SiW₁₂O₄₀)Cl·23H₂O (1-Ln, Ln = Ce, Pr, Nd) and [Cr₄Ln₄(μ₄-O)₄(μ₃-O)₄(C₈H₄O₄)₄(H₂O)₁₀](H₆SiW₁₂O₄₀)Cl₂·18H₂O (2-Ln, Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er) have been obtained. Single-crystal structural analyses show that 1-Ln and 2-Ln constitute the first cases of Cr–Ln heterometallic clusters stabilized by inorganic polyoxometalate anions and organic ligands. Optical spectra studies demonstrate that 1-Ln and 2-Ln are narrow-gap semiconductors with band gaps of about 1.5 eV. Magnetic investigation shows that compound 2-Dy is a potential single molecule magnet.