[α-AsW9O33]9− bridged hexagonal clusters of Ln(iii) showing field induced SMM behavior: experimental and theoretical insight

Abstract

Polyoxometalates (POM), as inorganic polydentate oxygen donors, provide binding opportunities for oxophilic lanthanide metal centers to construct novel Ln-substituted POM materials with exciting structures and attractive properties. Herein, we have reported four arsenotungstate [α-AsW₉O₃₃]⁹⁻ based lanthanide-containing polyoxometalates [Cs_xK_36–x{Ln₆(H₂O)₁₂(α-AsW₉O₃₃)₆}]·yH₂O (Ln = Er (1), Gd (2), Ho (3), and Tb (4)), which are synthesized in an alkaline medium. Complexes 1–3 are the dimeric structures of [Ln₃(H₂O)₆(α-AsW₉O₃₃)₃]¹⁸⁻ polyanions, whereas complex 4 is a hexamer of the polyanion [Tb (H₂O)₂(α-AsW₉O₃₃)]⁶⁻ as a building unit. In all the complexes, [α-AsW₉O₃₃]⁹⁻ units are staggered up and down and give rise to the chair conformation, where one [α-AsW₉O₃₃]⁹⁻ unit bridges two Ln(III) centers through four μ₂-oxygen and two terminal oxygen atoms, resulting in the hexagonal arrangement of lanthanides. The dynamic magnetic measurement indicates that only complex 1 exhibits slow relaxation of magnetization with an applied dc field (1500 Oe). To gain insight into the slow relaxation of magnetization in complex 1, the ligand-field parameters and the splitting of the ground-state multiplet of the Er(III) ions have been estimated. The ab initio calculation results confirm that the ground state wave function of these molecules (1, 3, and 4) is mainly composed of a mixture of m_J states, and the non-axial crystal field (CF) terms are more predominant than the axial CF term. The solid-state fluorescence spectra of 1–4 reveal that the photoexcitation O → M ligand-to-metal charge-transfer (LMCT) of arsenotungstate fragments is effectively quenched due to the spatial coordination environment around the Ln(III) ion.