Yann Molard

Influence of [Mo6Br8F6](2-) Cluster Unit Inclusion within the Mesoporous Solid MIL-101 on Hydrogen Storage Performance

The inclusion of (TBA)(2)Mo(6)Br(8)F(6) (TBA = tetrabutylammonium) containing [Mo(6)Br(8)F(6)](2-) cluster units within the pores of the mesoporous chromium carboxylate MIL-101 (MIL stand for Materials from Institut Lavoisier) has been studied. X-ray powder diffraction, thermal analysis, elemental analysis, solid-state NMR, and infrared spectroscopy have evidenced the successful loading of the cluster. In a second step, the hydrogen sorption properties of the model cluster loaded metal organic framework (MOF) system have been analyzed and compared to those of the pure MOF sample, through a combination of adsorption isotherms (77 K, room temperature), thermal desorption spectroscopy, and calorimetry (calculated and experimental) in order to evaluate the hydrogen storage efficiency of the cluster loading.

Surface Organometallic Chemistry of Main Group Elements: Selective Synthesis of Silica Supported [≡Si−OB(C6F5)3]−[HNEt2Ph]+

The reaction of the Lewis acid B(C(6)F(5))(3) with silanol groups of silica surfaces, dehydroxylated at different temperatures (300, 500, 700, and 800 degrees C), has been investigated in presence of the Bronsted base NEt(2)Ph. The structure of the resulting modified silica supports [triple bond Si-OB(C(6)F(5))(3)](-)[HNEt(2)Ph](+) (1) has been carefully identified by IR and multinuclear solid-state NMR spectroscopies, isotopic (2)H and (18)O labeling, elemental analysis, molecular modeling, and comparison with synthesized molecular models. Highly dehydroxylated silica surfaces were required to transform selectively each silanol group into unique [triple bond Si-OB(C(6)F(5))(3)](-)[HNEt(2)Ph](+) fragments. For lower dehydroxylation temperatures, two sorts of surface sites were coexisting on silica: the free silanol groups [triple bond SiOH] and the ionic species 1.

Synthesis of calix[4]arene podands bearing two and four histidine or glycine groups at the lower rim. Complexation properties towards cobalt(II) chloride

Abstract Four calix[4]arene podands displaying two or four glycine or histidine arms at the lower rim have been synthesised and fully characterised. Their coordinating behaviour towards cobalt(II) chloride has been investigated.

Direct Integration of Red-NIR Emissive Ceramic-like AnM6Xi8Xa6 Metal Cluster Salts in Organic Copolymers Using Supramolecular Interactions

Hybrid nanomaterials made of inorganic nanocomponents dispersed in an organic host raise an increasing interest as low-cost solution-processable functional materials. However, preventing phase segregation while allowing a high inorganic doping content remains a major challenge, and usual methods require a functionalization step prior integration. Herein, we report a new approach to design such nanocomposite in which ceramic-like metallic nanocluster compounds are embedded at 10 wt % in organic copolymers, without any functionalization. Dispersion homogeneity and stability are ensured by weak interactions occurring between the copolymer lateral chains and the nanocluster compound. Hybrids could be ink-jet printed and casted on a blue LED. This proof-of-concept device emits in the red-NIR area and generates singlet oxygen, O2 (1 Δg), of particular interest for lights, display, sensors or photodynamic based therapy applications.

Synthesis and characterization of magnetic-fluorescent composite colloidal nanostructures

In this communication, we report fluorescent and magnetic bifunctional structures in the nanoscale range. The synthesis and characterisation of various colloidal nanostructures as Y3Fe5-xAlxO12-TRITC, gamma-Fe2O3-Cs2Mo6Br14@SiO2 and Fe2O3-QDs will be presented. At the outset, the first synthesis of aluminium substituted YAIG (Y3Fe5-xAlxO12) by the citrate gel process and its surface modification by TRITC through grafting of 3-aminopropyltrimethoxysilane (g-APS) for biology-related labelling will be reported. Secondly, the synthesis of nanoparticles under restricted environments offered by water-in-oil microemulsions provides excellent control over particle size and shape and interparticle spacing. These environments have been used in the synthesis of silica nanoparticles (50 nm) with magnetic nanocrystals core surrounded by optically active nanoclusters. Finally, we will describe the preparation of composite magnetic QD bioconjugable micelles by simultaneous encapsulation of hydrophobic CdSe/ZnS QDs (2-4 nm) and magnetic gamma-Fe2O3 nanoparticles (3-4 nm) into micelles of synthetic functional PEG amphiphiles bearing a bioactivable terminal group.

Tailoring the self-assembling abilities of functional hybrid nanomaterials: from rod-like to disk-like clustomesogens based on a luminescent {Mo6Br8}4+ inorganic cluster core

Self-organizing processes are elegant ways to generate and control the nanostructuration of hybrid materials. We describe in this work the synthesis, self-organizing abilities and photo-physical properties of (nBu4N)2[Mo6Bri8(L)a6] clustomesogens containing 18 cyanobiphenyl (CB) mesogenic moieties spread equally around the metallic scaffold via aliphatic spacers. By controlling the spacer length and thus the mesogenic density around the rigid inorganic bulky scaffold, we tailored the morphology of hybrid supermolecular building blocks from rod-like to disk-like which strongly influenced their self-organizing abilities. The photophysical properties of hybrids were investigated in their glassy state and in solution. Temperature studies reveal different behaviours depending on the hybrid nanostructuration. Despite their isotropic nature, octahedral clusters offer numerous possibilities in the design of self-assembled hybrid materials showing strong luminescence properties, which is of particular interest in the fields of optics or optoelectronics.