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A new series of lanthanide-based complexes with a bis(hydroxy)benzoxaborolone ligand Synthesis, crystal structure, and magnetic and optical properties

Abstract : Reactions, under hydrothermal conditions, between lanthanide chlorides and the sodium salt of 2-carboxyphenylboronic acid lead to a series of lanthanide-based complexes with general chemical formula [Ln2(C7H5O2)4(C7O4H6B)2·4H2O] with Ln = Eu–Dy. During the synthetic process, the 2-carboxyphenylboronate ligand decomposes leading to benzoate (C7H5O2) and bis(hydroxy)benzoxaborolone (C7O2H6B). The crystal structure was solved on the basis of the Tb-derivative. It crystalizes in the triclinic system, space group P[1 with combining macron] (n° 2) with a = 9.3329(13) Å, b = 16.012(2) Å, c = 16.212(2) Å, α = 107.789(5)°, β = 90.226(5)°, γ = 97.585(5)°, V = 2284.16(52) Å3 and Z = 2. Its crystal structure can be described on the basis of di-lanthanides entities surrounded by ligands. Compounds that constitute this series are thermally stable up to 190 °C. Solid-state luminescence properties have been studied in detail. The magnetic properties of the Dy-derivative have also been explored. It exhibits single molecule magnet behavior. Single crystals of the sodium salt of 2-carboxyphenylboronic acid with chemical formula [Na(C7O4H6B)(H2O)]∞ have also been obtained during this study. This compound crystallizes in the orthorhombic system, space group P212121 (n° 19) with a = 4.5881(13) Å, b = 6.5905(16) Å, c = 29.644(8) Å, V = 897.0(4) Å3 and Z = 4. Its crystal structure is 2D and can be described as zigzag chains of sodium 2-carboxyphenylboronate bound to each other by coordination water molecules.
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A. Abdallah, M. Puget, C. Daiguebonne, Y. Suffren, Guillaume Calvez, et al.. A new series of lanthanide-based complexes with a bis(hydroxy)benzoxaborolone ligand Synthesis, crystal structure, and magnetic and optical properties. CrystEngComm, Royal Society of Chemistry, 2020, 22 (11), pp.2020-2030. ⟨10.1039/c9ce01592b⟩. ⟨hal-02536598⟩

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