Reactive Magnesium Nanoparticles to Perform Reactions in Suspension.

Zerovalent magnesium (Mg(0)) nanoparticles are prepared in the liquid phase (THF) by reduction of MgBr2 either with lithium naphthalenide ([LiNaph]) or lithium biphenyl ([LiBP]). [LiBP]-driven reduction results in smaller Mg(0) nanoparticles (10.3±1.7 nm) than [LiNaph]-driven reduction (28.5±4 nm). The as-prepared Mg(0) nanoparticles are monocrystalline (d101=245±5 pm) for both types of reduction. Their reactivity is probed by liquid-phase reaction (THF, toluene) in suspension near room temperature (20-120 °C) with 1-bromoadamantane (AdBr), chlortriphenylsilane (Ph3SiCl), trichlorphenylsilane (PhSiCl3), 9H-carbazole (Hcbz), 7-azaindole (Hai), 1,8-diaminonaphthalene (H4nda) and N,N'-bis(α-pyridyl)-2,6-diaminopyridine (H2tpda) as exemplary starting materials. The reactions result in the formation of 1,1'-biadamantane (1), [MgCl2(thf)2]×Ph6Si2 (2), [Mg9(thf)14Cl18] (3), [Mg(cbz)2(thf)3] (4), [Mg4O(ai)6]×1.5 C7H8 (5), [Mg4(H2nda)4(thf)4] (6) and [Mg3(tpda)3] (7) with 40-80 % yield. 1 and 2 show the reactivity of Mg(0) nanoparticles for C-C and Si-Si coupling reactions with sterically demanding starting materials. 3-7 represent new coordination compounds using sterically demanding N-H-acidic amines as starting materials. The formation of multinuclear Mg2+ complexes with multidentate ligands illustrates the potential of the oxidative approach to obtain novel compounds with Mg(0) nanoparticles in the liquid phase.

Monitoring nanoparticle dissolution via fluorescence-colour shift.

[La(OH)]2+[ICG]-2 and [La(OH)]2+2[PTC]4- inorganic-organic hybrid nanoparticles (IOH-NPs) with indocyanine green (ICG) and perylene-3,4,9,10-tetracarboxylate (PTC) as fluorescent dye anions are used for emission-based monitoring of the dissolution of nanoparticles. Whereas ICG shows a deep red emission in the solid [La(OH)]2+[ICG]-2 IOH-NPs, the emission of PTC in the solid [La(OH)]2+2[PTC]4- IOH-NPs is completely quenched due to π-stacking. After nanoparticle dissolution, the emission of freely dissolved ICG is weak, whereas freely dissolved PTC shows intense green emission. We report on the synthesis of IOH-NPs and nanoparticle characterization as well as on the fluorescence properties and how to avoid undesirable energy transfer between different fluorescent dyes. The emission shift from red (intact solid nanoparticles) to green (freely dissolved dye anions), indicating nanoparticle dissolution, is shown for aqueous systems and verified in vitro. Based on this first proof-of-the-concept, the IOH-NP marker system can be interesting to monitor nanoparticle dissolution in cells and tissues of small animals and to evaluate cell processes and/or drug-delivery strategies.

Facet-, composition- and wavelength-dependent photocatalysis of Ag2MoO4.

Faceted ß-Ag2MoO4 microcrystals are prepared by controlled nucleation and growth in diethylene glycol (DEG) or dimethylsulfoxide (DMSO). Both serve as solvents for the liquid-phase synthesis and surface-active agents for the formation of faceted microcrystals. Due to its reducing properties, truncated ß-Ag2MoO4@Ag octahedra are obtained in DEG. The synthesis in DMSO allows avoiding the formation of elemental silver and results in ß-Ag2MoO4 cubes and cuboctahedra. Due to its band gap of 3.2 eV, photocatalytic activation of ß-Ag2MoO4 is only possible under UV-light. To enable ß-Ag2MoO4 for absorption of visible light, silver-coated ß-Ag2MoO4@Ag and Ag2(Mo0.95Cr0.05)O4 with partial substitution of [MoO4]2- by [CrO4]2- were prepared, too. The photocatalytic activity of all the faceted microcrystals (truncated octahedra, cubes, cuboctahedra) and compositions (ß-Ag2MoO4, ß-Ag2MoO4@Ag, ß-Ag2(Mo0.95Cr0.05)O4) is compared with regard to the photocatalytic decomposition of rhodamine B and the influence of the respective faceting, composition and wavelength.