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 [CsxK36-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 mJ 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.

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

Polyoxoarsenotungstate in Oxalis Triangularis Arrangement Favors Slow Magnetic Relaxation for Both Prolate and Oblate Lanthanides

A new type of turn-off photoluminescence (PL) humidity sensor based on a water-responsive anhydrous alkali lanthanide-free [SbW6O24]7- polyoxometalate (POM) is reported. Na7[SbW6O24](NaSbW6) was recently obtained by heating its parent hydrate...

Na7[SbW6O24]: a new type of turn-off luminescence humidity sensor based on a lanthanide-free polyoxometalate

Three new water-responsive luminescent lanthanide-free polyoxometalate (Ln-free POM) materials Na7[SbW6O24], K5Na2[SbW6O24] and K7[SbW6O24] were prepared by thermally dehydrating the known compounds Na7[SbW6O24]·16H2O, K5Na2[SbW6O24]·12H2O, and a new one K7[SbW6O24]·6H2O. The isostructural...

/pdf/new-alkali-lanthanide-free-polyoxometalates-with-remarkable-1gbu148d.pdf

New Alkali Lanthanide-free Polyoxometalates with Remarkable Water-Responsive Turn-Off-On Luminescence Properties

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New Alkali Lanthanide-free Polyoxometalates with Remarkable Water-Responsive Turn-Off-On Luminescence Properties