Wilfried-Solo Ojo

InP/ZnS Nanocrystals: Coupling NMR and XPS for Fine Surface and Interface Description

Advanced (1)H, (13)C, and (31)P solution- and solid-state NMR studies combined with XPS were used to probe, at the molecular scale, the composition (of the core, the shell, and the interface) and the surface chemistry of InP/ZnS core/shell quantum dots prepared via a non-coordinating solvent strategy. The interface between the mismatched InP and ZnS phases is composed of an amorphous mixed oxide phase incorporating InPO(x) (with x = 3 and predominantly 4), In(2)O(3), and InO(y)(OH)(3-2y) (y = 0, 1). Thanks to the analysis of the underlying reaction mechanisms, we demonstrate that the oxidation of the upper part of the InP core is the consequence of oxidative conditions brought by decarboxylative coupling reactions (ketonization). These reactions occur during both the core preparation and the coating process, but according to different mechanisms.

Highly fluorinated aryl-substituted tris(indazolyl)borate thallium complexes: diverse regiochemistry at the B-N bond.

The synthesis and characterization (mainly by (19)F NMR and X-ray diffraction) of highly fluorinated aryl-4,5,6,7-tetrafluoroindazoles and their corresponding thallium hydrotris(indazolyl)borate complexes are reported [aryl = phenyl, pentafluorophenyl, 3,5-dimethylphenyl, 3,5-bis(trifluoromethyl)phenyl]. Thanks to N-H···N hydrogen bonds, the indazoles crystallize as dimers that pack differently depending on the nature of the aryl group. The thallium hydrotris(indazolyl)borate complexes Tl[Fn-Tp(4Bo,3aryl)] resulting from the reaction of aryl-4,5,6,7-tetrafluoroindazoles [aryl = phenyl, 3,5-dimethylphenyl, 3,5-bis(trifluoromethyl)phenyl] with thallium borohydride adopt overall C(3v) symmetry with the indazolyl groups bound to boron via their N-1 nitrogen in a conventional manner. When the perfluorinated pentaphenyl-4,5,6,7-tetrafluoroindazole is reacted with thallium borohydride, a single regioisomer of C(s) symmetry having one indazolyl ring bound to boron via its N-2 nitrogen, TlHB(3-pentafluorophenyl-4,5,6,7-tetrafluoroindazol-1-yl)(2)(3-pentafluorophenyl-4,5,6,7-tetrafluoroindazol-2-yl) Tl[F27-Tp((4Bo,3C6F5)*)], is obtained for the first time. Surprisingly, the perfluorinated dihydrobis(indazolyl)borate complex Tl[F(18)-Bp(3Bo,3C6F5)], an intermediate on the way to the hydrotris(indazolyl)borate complex, has C(s) symmetry with two indazolyl rings bound to boron via N-2. The distortion of the coordination sphere around Tl and the arrangement of the complexes in the crystal are discussed.

Stoichiometry-controlled FeP nanoparticles synthesized from a single source precursor

Phase-pure FeP nanoparticles (NPs) have been synthesized through low temperature thermolysis of the single source precursor [(CO)4Fe(PH3)]. Examination of the mechanism demonstrates the central role of the labile CO ligands and the weak P-H bonds to yield stoichiometry controlled FeP materials.

Perfluorinated 1H-indazoles and hydrotris(indazol-1-yl)borates. Supramolecular organization and a new synthetic procedure to form scorpionate ligands

This paper describes the syntheses and full characterization of perfluorinated 1H-indazoles 2–5 and hydrotris(indazolyl)borate thallium complexes 6–9 that contain linear perfluoroalkyl chains varying from two to six carbon atoms in the 3-position. In the solid state, the perfluorinated 1H-indazoles exhibit supramolecular structures that depend on the length of the perfluoroalkyl chain. A catemer of order 3 is observed for the CF2CF3 derivative 2 (chiral space group P32), catemers of order 2 are observed for the C3F7 and C4F9 derivatives 3 (chiral space group P212121, one type of helix in the unit cell) and 4 (space group P21/n, two types of helices in the unit cell), respectively, and stacks of dimers are observed for the indazole with the longer C6F13 chain 5 (space group P21/c). The perfluorinated hydrotris(indazolyl)borate thallium complexes 6–9 [TlFn–Tp4Bo,3Rf] have been obtained by a new reaction based on the reaction of HBBr2 (generated in situ from BBr3 and Et3SiH) with the indazolates of 2–5 followed by cation exchange. The X-ray crystal structure of [TlF33–Tp4Bo,3C3F7] 7 shows that, in addition to coordination to the three nitrogens, the thallium is buried in a nest of fluorines with seven short intramolecular Tl⋯F contacts with the pendant perfluoropropyl chains. The potential of these highly fluorinated molecules to act as ligands is highlighted.

Transition-metal complexes containing parent phosphine or phosphinyl ligands and their use as precursors for phosphide nanoparticles.

P-H functional transition-metal complexes were synthesized without using hazardous PH3 gas in good yields by photolysis of the transition-metal carbonyl complexes M(CO)(6-x) (M = Cr, W, Fe; x = 0, 1) in tetrahydrofuran followed by reaction with P2(SiMe3)4 and subsequent methanolysis to give the bridging complexes [(CO)(x)M(μ-PH2)]2 (M = Fe, x = 3 (1), M = Cr, x = 4 (2a), M = W, x = 4 (2b)). The photolysis of [(CO)4M(μ-PH2)]2 (M = Cr (2a), M = W (2b)) with P(SiMe3)3 was applied followed by methanolysis to synthesize the PH2 bridging transition-metal binuclear complexes with terminal PH3 groups. The products [(CO)4M(μ-PH2)2M(CO)3(PH3)] (M = Cr (3a), M = W (3b)) and [(CO)4W(μ-PH2)2W(CO)2(PH3)2] (4b) were isolated in moderate yield. Another synthetic approach to this type of compounds is the direct photolysis of the complexes [(CO)3M(PH3)3] (M = Cr (5a), M = W (5b)). The products were comprehensively characterized by (31)P NMR and IR spectroscopy as well as by X-ray structural analysis. Additionally, the relevancy of 2a as single source precursor for the synthesis of stoichiometry-controlled CrP nanoparticles has been demonstrated.

Low temperature MIR to submillimeter mass absorption coefficient of interstellar dust analogues - I. Mg-rich glassy silicates

A wealth of data from the Herschel and Planck satellites and now from ALMA, revealing cold dust thermal emission, is available for astronomical environments ranging from interstellar clouds, cold clumps, circumstellar envelops, and protoplanetary disks. The interpretation of these observations relies on the understanding and modeling of cold dust emission and on the knowledge of the dust optical properties. The aim of this work is to provide astronomers with a set of spectroscopic data of realistic interstellar dust analogues that can be used to interpret the observations. Glassy silicates of mean composition (1-x)MgO - xSiO2 with x = 0.35, 0.40 and 0.50 were synthesized. The mass absorption coefficient (MAC) of the samples was measured in the spectral domain 30 - 1000

Low-temperature MIR to submillimeter mass absorption coefficient of interstellar dust analogues - II. Mg and Fe-rich amorphous silicates

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Thermoresponsive gold nanoshell@mesoporous silica nano-assemblies: an XPS/NMR survey

m for grain temperature in the range 300 K - 10 K and at room temperature in the 5 - 40

Silica coated iron nanoparticles: synthesis, interface control, magnetic and hyperthermia properties

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CCDC 982670: Experimental Crystal Structure Determination

m domain. We find that the MAC of all samples varies with the grains temperature. In the FIR/submm, and above 30K, the MAC value at a given wavelength increases with the temperature as thermally activated absorption processes appear. The studied materials exhibit different and complex behaviors at long wavelengths (lambda