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Francis Sécheresse

Publications and source records attributed to Francis Sécheresse.

8 recordsLinked to original sources

Solid-State and solution studies of [Ln(n)(SiW11O39)] polyoxoanions: an example of building block condensation dependent on the nature of the rare earth.

The reactivity of the [alpha-SiW(11)O(39)](8-) monovacant polyoxometalate with lanthanide has been investigated for four different trivalent rare-earth cations (Ln = Nd(III), Eu(III), Gd(III), Yb(III)). The crystal structures of KCs(4)[Yb(alpha-SiW(11)O(39))(H(2)O)(2)] x 24H(2)O (1), K(0.5)Nd(0.5)[Nd(2)(alpha-SiW(11)O(39))(H(2)O)(11)] x 17H(2)O (2a), and Na(0.5)Cs(4.5)[Eu(alpha-SiW(11)O(39))(H(2)O)(2)] x 23H(2)O (3a) are reported. The solid-state structure of compound 1 consists of linear wires built up of [alpha-SiW(11)O(39)](8-) anions connected by Yb(3+) cations, while the linkage of the building blocks by Eu(3+) centers in 3a leads to the formation of zigzag chains. In 2a, dimeric [Nd(2)(alpha-SiW(11)O(39))(2)(H(2)O)(8)](10-) entities are linked by four Nd(3+) cations. The resulting chains are connected by lanthanide ions, leading to a bidimensional arrangement. Thus, the dimensionality, the organization of the polyoxometalate building units, and the Ln/[alpha-SiW(11)O(39)](8-) ratio in the solid state can be tuned by choosing the appropriate lanthanide. The luminescent properties of compound 3a have been studied, showing that, in solution, the polymer decomposes to give the monomeric complex [Eu(alpha-SiW(11)O(39))(H(2)O)(4)](5-). The lability of the four exogenous ligands connected to the rare earth must allow the functionalization of this lanthanide polyanion.

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A new two-dimensional molybdenum(V) nickel phosphate built up of [H18(Mo16O32)Ni16(PO4)26(OH)6(H2O)8]18- wheels.

The new molybdenum(V) nickel phosphate Na(6)Ni(6)[(Mo(2)O(4))(8)Ni(16)(H(2)PO(4))(4)(HPO(4))(10)(PO(4))(12)(OH)(6)(H(2)O)(8)].66H(2)O (1) was synthesized hydrothermally. The structure (orthorhombic, space group Cccm; a = 23.999(4), b = 36.595(6), c = 20.445(4) A) was solved from single-crystal data. The framework structure of 1 consists of anionic inorganic sheets formed by the linkages of large polyoxomolybdate rings via nickel(II) octahedra. Charge-compensating sodium atoms are interleaved between the sheets. Magnetic studies of compound 1 revealed that among the 22 nickel(II) centers, 10 are interacting. The chi(M)T = f(T) curve can be fitted using the dinuclear expression appropriate to the HDVV isotropic exchange Hamiltonian H = -2JS(1).S(2), with S(1) = S(2) = 1 and J = -24.1 cm(-)(1), showing that nickel is antiferromagnetically coupled within Ni(2) pairs.

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Cyclic molecular materials based on [M2O2S2]2+ cores (M = Mo or W).

The purpose of this article is to illustrate how conventional precursors can serve, when used with a drop of imagination, to the synthesis of sophisticated inorganic rings and wheels. The self-condensation of the [M2O2S2]2+ fragments under acido-basic process produces, in the presence or absence of guest species, linear enchainment restricted to discrete cyclic entities. This approach was revealed to be a highly fruitful strategy for developing an extended family of compounds, differing in their nuclearity, size and shape, and the nature of the encapsulated guest molecule. Indeed, the resulting cycles delimit a cationic open cavity, which can be filled by neutral polar molecules such as aquo ligands or anionic molecules such as phosphates, polycarboxylates and even metalates. The flexibility of the rings is at the origin of interesting host-guest properties: the deformation (symmetry) and the adaptation (nuclearity) of the inorganic cycle are directly related to the size and the coordination requirements of the encapsulated substrate. The versatility of the metal coordination, octahedral or square pyramidal, confers dynamic properties to the ring. In the solid state, molecular rings assemble in striking 3-D networks based on direct cation-anion connections. Alkali cations are arranged in pillars or layers for anchoring the anionic rings.

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Synthesis, X-ray and neutron diffraction characterization, and ionic conduction properties of a new oxothiomolybdate Li3[Mo8S8O8(OH)8[HWO5(H2O)]] x 18H2O.

The new oxothiomolybdate anion [Mo8S8O8(OH)8[HWO5(H2O)]]3- (denoted HMo8W3-) has been synthesized in aqueous solution by an acido-basic condensation reaction. Four (Mo(V)2S2O2) building blocks are connected through hydroxo bridges around a central [W(VI)O6] octahedron. X-ray and neutron diffraction studies have been performed on single crystals of the lithium salt Li3[Mo8S8O8(OH)8[HWO5(H2O)]] x 18H2O (Li3HMo8W x 18H2O) in an aqueous grown from HMo8W3- solution of LiCl (1 M). The neutron diffraction experiment enabled us to locate both the protons and the lithium ions. In the structure of Li3HMo8W x 18H20, ring-shaped anions interleaved by a cluster of disordered hydrogen-bonded water molecules stack on top of each other along lithium pillars. The lithium columns are formed by alternating edge-sharing octahedra and tetrahedra, with one lithium site in four being totally vacant. Ionic conductivity measurements on pressed pellets have shown that Li3HMo8W x 18H2O is a good ionic conductor at room temperature (sigma = 10(-5) S cm(-1)), but the ionic conductivity on single crystals is smaller by two orders of magnitude and is isotropic; this suggests the main path of conduction involves surface protons rather than lithium ions of the bulk.

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