Crystal structure, physico-chemical and catalytic properties of two organic–inorganic hybrid polyoxometallate-based lanthanide complexes

Abstract

International audienceTwo organic–inorganic compounds based on Keggin anions and lanthanide ions have been synthesized. Their chemical formulae are [Eu(C2H6SO)8][PMo12O40] (1) and [Er(C2H6SO)8][PMo12O40]·2(C2H6SO)·1/2H2O (2), respectively. They have been structurally characterized by single-crystal X-ray diffraction, IR, thermal analyses and cyclic voltammetry measurements. 1 and 2 crystallize in the space groups View the MathML sourceP1¯ and P21/c, respectively. Their catalytic activity toward organic dyes is quite sizeable since the target removal after 120 min is about 78.6% in the presence of the system [Eu(C2H6SO)8][PMo12O40]/H2O2 and 60.3% in the presence of the system [Er(C2H6SO)8][PMo12O40]·2(C2H6SO)·1/2H2O/H2O2

Syntheses, Polymorphic Transformations, and Functions of Ionic Crystals Based on Mononuclear Bismuth(III) Complexes and Polyoxometalates

“…3À . [37] The molecular structure of [Bi(DMSO) 8 ] 3 + well agreed with a previous report: [29] The Bi 3 + center was eight coordinated by oxygen atoms belonging to different DMSO molecules resulting in a triangular dodecahedron (Figure 1c S6). The void volume of 2 a was 13.0% (975.6 Å 3 ) of the unit cell, and two DMSO and one H 2 O molecules were contained in the void.…”

“…The bismuth(III) center exhibited triangular dodecahedron, square antiprism, or pseudo-cubic eight-coordination geometries with DMSO or DMF as ligands. While ionic crystals isostructural with 1, 2a, and 3 have been previously reported with different metal ions (Eu 3 + , Er 3 + , Bi 3 + ), [30,37] we wish to emphasize that this is the first example of isolating all these structures as polymorphs based on bismuth(III). The ionic crystals showed polymorphic transformation, and the proton conductivity depended on the types of ligands and/or the porosity of the crystal lattice.…”

“…The void volume of 2 a was 13.0% (975.6 Å 3 ) of the unit cell, and two DMSO and one H 2 O molecules were contained in the void. The crystal structure of 2 a (Figure 3) was analogous to that of an ionic crystal composed of [Er(DMSO) 8 ] 3+ and [α‐PMo 12 O 40 ] 3− [37] . Notably, the coordination of DMSO molecules in 2 a was different from that of 1 : [Bi(DMSO) 8 ] 3+ in 2 a can be described as a square antiprism with D 4d symmetry, while that in 1 is a triangular dodecahedron with D 2d symmetry (Figure 1c).…”

“…The crystal structure of 2 a (Figure 3) was analogous to that of an ionic crystal composed of [Er(DMSO) 8 ] 3 + and [α-PMo 12 O 40 ] 3À . [37] Nota-bly, the coordination of DMSO molecules in 2 a was different from that of 1: [Bi(DMSO) 8 ] 3 + in 2 a can be described as a square antiprism with D 4d symmetry, while that in 1 is a triangular dodecahedron with D 2d symmetry (Figure 1c S8). The crystal structure of 3 is shown in Figure 5.…”

“…The crystal structure of 1 in the bc-and ac-planes is shown in Figure 2: Oppositely charged [Bi(DMSO) 8 ] 3 + and [α-PW 12 O 40 ] 3À were arranged alternately in the crystal lattice. The crystal structure of 1 was analogous to that of an ionic crystal composed of [Eu(DMSO) 8 ] 3 + and [α-PMo 12 O 40 ]3À [37]. The molecular structure of [Bi(DMSO) 8 ] 3 + well agreed with a previous report:[29] The Bi 3 + center was eight coordinated by oxygen atoms belonging to different DMSO molecules resulting in a triangular dodecahedron (Figure1c), and the average BiÀ O distance was 2.44 Å.…”