Direct Synthesis of Two-Dimensional SnSe and SnSe2 through Molecular Scale Preorganization.

Two-dimensional tin monoselenide (SnSe) and tin diselenide (SnSe2) materials were efficiently produced by the thermolysis of molecular compounds based on a new class of seleno-ligands. Main group metal chalcogenides are of fundamental interest due to their layered structures, thickness-dependent modulation in electronic structure, and small effective mass, which make them attractive candidates for optoelectronic applications. We demonstrate here the synthesis of stable tin selenide precursors by in situ reductive bond cleavage in the dimeric diselenide ligand (SeC2H4N(Me)C2H4Se)2 in the presence of SnCl4. New molecular precursors [SnIV(SeC2H4N(Me)C2H4Se)2], [SnIVCl2(SeC2H4N(Me)C2H4Se)], and [SnIV(SC2H4N(Me)C2H4S)(SeC2H4N(Me)C2H4Se)] were thoroughly characterized by multinuclear magnetic resonance studies and single-crystal X-ray diffraction analysis that revealed the Sn(IV) center to be octahedrally coordinated by two tridentate dianionic chelating ligands or trigonally pyramidally coordinated by one chelating ligand and two chlorido ligands. Preorganization of metal-selenium bonds in both compounds offered direct and reproducible synthetic access to two-dimensional tin chalcogenides (SnSe and SnSe2) via simple adjustment of the pyrolysis temperature. Additionally, SnSe2 and SnSxSe2-x particles could be successfully synthesized by microwave-assisted decomposition of the molecular precursors, which was unambiguously corroborated by both experimental and computational analyses that explained the formation of a selenium rich SnSxSe2-x phase from a single molecular precursor containing both Sn-Se and Sn-S bonds.

Single source precursor route to nanometric tin chalcogenides.

Low-temperature solution phase synthesis of nanomaterials using designed molecular precursors enjoys tremendous advantages over traditional high-temperature solid-state synthesis. These include atomic-level control over stoichiometry, homogeneous elemental dispersion and uniformly distributed nanoparticles. For exploiting these advantages, however, rationally designed molecular complexes having certain properties are usually required. We report here the synthesis and complete characterization of new molecular precursors containing direct Sn-E bonds (E = S or Se), which undergo facile decomposition under different conditions (solid/solution phase, thermal/microwave heating, single/mixed solvents, varying temperatures, etc.) to afford phase-pure or mixed-phase tin chalcogenide nanoflakes with defined ratios.

Molecular Routes to Two-Dimensional Metal Dichalcogenides MX2 (M = Mo, W; X = S, Se).

New synthetic access to two-dimensional transition metal dichalcogenides (TMDCs) is highly desired to exploit their extraordinary semiconducting and optoelectronic properties for practical applications. We introduce here an entirely novel class of molecular precursors, [MIV(XEtN(Me)EtX)2] (MIV = MoIV, WIV, X = S, Se), enabling chemical vapor deposition of TMDC thin films. Molybdenum and tungsten complexes of dianionic tridentate pincer-type ligands (HXEt)2NR (R = methyl, tert-butyl, phenyl) produced air-stable monomeric dichalcogenide complexes, [W(SEtN(Me)EtS)2] and [Mo(SEtN(Me)EtS)2], displaying W and Mo centers in an octahedral environment of 4 S and 2 N donor atoms. Owing to their remarkable volatility and clean thermal decomposition, both Mo and W complexes, when used in the chemical vapor deposition (CVD) process, produced crystalline MoS2 and WS2 thin films. X-ray diffraction analysis and atomic-scale imaging confirmed the phase purity and 2D structural characteristics of MoS2 and WS2 films. The new set of ligands presented in this work open ups convenient access to a scalable and precursor-based synthesis of 2D transition metal dichalcogenides.

Single-source precursors for alloyed gold-silver nanocrystals - a molecular metallurgy approach.

Multiple silver(I)-aurates(I) have been prepared by salt metathesis reactions that act as efficient single-source precursors to colloidal gold silver alloys with the highest possible atom economy in the chemical synthesis of nanostructures. The CF3 group present on the Au cation acts as an in situ reducing agent and can be converted into CO ligands by simple hydrolysis. This ligand-mediated activation and subsequent decomposition of metal-organic precursors impose a molecular control over the nucleation process, producing homogeneously alloyed (Ag-Au) nanoparticles with an atomic Au:Ag ratio of 1:1. The concept also works for the Au-Cu system and acts as a pointer to replace Au (Ag) with less expensive (Cu) metals.

Molecular Co(II) and Co(III) heteroarylalkenolates as efficient precursors for chemical vapor deposition of Co3O4 nanowires.

Two new cobalt precursors, Co(II)(PyCHCOCF3)2(DMAP)2 (1) and Co(III)(PyCHCOCF3)3 (2), based on Co(II) and Co(III) centers were synthesized using a redox active ligand system. The different chemical configurations of 1 and 2 and differential valence states of cobalt were confirmed by crystal structure determination and comprehensive analytical studies. Whereas 1 could not be studied by NMR due to the paramagnetic nature of the central atom, 2 was unambiguously characterized by multinuclear 1D and 2D NMR experiments in solution. Both compounds are efficient precursors for catalyst-free growth of Co3O4 nanowires on Si and Al2O3 substrates by a chemical vapor deposition process. The different valence states of cobalt species influenced their chemical decomposition pathways in the gas phase; for instance, 1 was partially oxidized (Co(2+) → Co(3+)), and 2 underwent reduction (Co(3+) → Co(2+)) to form pure cobaltite in both cases that verified the metal-ligand redox interplay. Co3O4 nanowires with nanometric diameters (50-100 nm) were obtained irrespective of the chosen cobalt precursor. Investigations on the humidity sensing behavior of CVD deposits demonstrated their potential as promising sensor materials.

[(CF3)4Au2(C5H5N)2]--a new alkyl gold(II) derivative with a very short Au-Au bond.

A new gold(II) species [(CF(3))(4)Au(2)(C(5)H(5)N)(2)] with a very short unsupported Au-Au bond (250.62(9) pm) was generated by photo irradiation of a silver aurate, [Ag(Py)(2)][Au(CF(3))(2)], unambiguously characterized by (19)F and (109)Ag NMR studies.