Chemical synthesis of air-stable manganese nanoparticles.

Elemental manganese has a complex crystal structure and unusual magnetic properties, making it an intriguing target for exploration in nanocrystalline form. However, because of its oxophilicity and the difficulty in reducing soluble metal salts to elemental Mn using the most common solution-phase reducing agents, it has been challenging to synthesize and stabilize elemental Mn nanoparticles using solution chemistry methods. Here we report the chemical synthesis of alpha-Mn nanoparticles using n-butyllithium as a reducing agent. The nanoparticles have been characterized by powder XRD, TEM, electron diffraction, infrared spectroscopy (DRIFT), XPS, and SQUID magnetometry. An amorphous manganese oxide layer bound by oleate ligands helps to render the nanoparticles air-stable. The oxide-coated alpha-Mn nanoparticles are paramagnetic.

On-wire conversion chemistry: engineering solid-state complexity into striped metal nanowires using solution chemistry reactions.

Multisegment template-grown metal nanowires have become important one-dimensional materials for a variety of applications in chemistry, physics, engineering, biology, and medicine. Segmented nanowires are traditionally fabricated in anodic alumina membranes using electrodeposition, and this technique is applicable to a range of metals, alloys, and semiconductors. Here we report an alternative and simple solution chemistry strategy for incorporating multimetal components of controllable length and composition into template-grown metal nanowires. By reacting membrane-confined nanowires with metal salt solutions under reducing conditions, site-specific diffusion occurs to convert one or both nanowire tips or the entire nanowire into a variety of multimetal phases. Platinum-based intermetallic compounds were chosen as targets for demonstrating the feasibility of the on-wire conversion chemistry.

Orthogonal reactivity of metal and multimetal nanostructures for selective, stepwise, and spatially-controlled solid-state modification.

Chemists rely on a toolbox of robust chemical transformations for selectively modifying molecules with spatial and functional precision to make them more complex in a controllable and predictable manner. This manuscript describes proof-of-principle experiments for a conceptually analogous strategy involving the selective, stepwise, and spatially controlled modification of inorganic nanostructures. The key concept is orthogonal reactivity: one component of a multicomponent system reacts with a particular reagent under a specific set of conditions while the others do not, even though they are all present together in the same reaction vessel. Using the chemical conversion of metal nanoparticles into intermetallic, sulfide, and phosphide nanoparticles as representative examples, the concept of orthogonal reactivity is defined and demonstrated for a variety of two- and three-component nanoscale systems. First, solution-phase reactivity data are presented and collectively analyzed for the reaction of metal nanoparticles (Ni, Cu, Rh, Pd, Ag, Pt, Au, Sn) with several metal salt and elemental reagents (Bi, Pb, Sb, Sn, S). From these data, several two- and three-component orthogonal systems are identified. Finally, these results are applied to the spatially selective chemical modification of lithographically patterned surfaces and striped template-grown metal nanowires.

Determination of absolute configuration of chiral hemicage metal complexes using time-dependent density functional theory.

Time-dependent density functional theory (TD-DFT) is applied to the UV-vis absorption and circular dichroism (CD) spectra of a series of transition metals (M=Ru, Zn, Fe) complexed with an enantiopure hemicage ligand, (-)-(5R,5'R,5' 'R,7R,7'R,7' 'R,8S,8'S,8' 'S)-8,8',8' '-[(2,4,6-trimethyl-1,3,5-benzenetriyl)tris(methylene)]tris[5,6,7,8-tetrahydro-6,6-dimethyl-3-(2-pyridinyl)-5,7-methanoisoquinoline (1). The electronic spectra of the Ru and Fe complexes contain two regions, one featuring low-energy 1MLCT transitions and the other higher energy 1LC transitions; the Zn analog possesses only the 1LC transitions due to its filled 3d shell. TD-DFT is able to identify correctly these transitions in the spectra, as well as to reproduce experimental spectra accurately, with regard to both the transition energies and the relative intensities of the different transitions. Additionally, it is possible to use TD-DFT to assign the absolute configuration at the metal center with high confidence by matching the experimental and calculated spectra.

Synthesis, separation, and circularly polarized luminescence studies of enantiomers of iridium(III) luminophores.

A family of heteroleptic (C;N)2Ir(acac) and homoleptic fac-Ir(C;N)3 complexes have been synthesized and their photophysical properties studied (where C;N = a substituted 2-phenylpyridine and acac = acetylacetonate). The neutral Delta and Lambda complexes were separated with greater than 95% enantiomeric purity by chiral supercritical fluid chromatography, and the solution circular dichroism and circularly polarized luminescence spectra for each of the enantio-enriched iridium complexes were obtained. The experimentally measured emission dissymmetries (gem) for this series compared well with predicted values provided by time-dependent density functional theory calculations. The discovered trend further showed a correlation with the dissymmetries of ionic, enantiopure hemicage compounds of Ru(II) and Zn(II), thus demonstrating the applicability of the model for predicting emission dissymmetry values across a wide range of complexes.

Synthesis and characterization of hemicage 8-hydroxyquinoline chelates with enhanced electrochemical and photophysical properties.

A new hexadentate, tripodal 8-hydroxyquinoline ligand (QH3) and its trivalent metal chelates (MQ, M=Al3+, Ga3+, In3+) with hemicage structures have been prepared and the electrochemical and photophysical properties systematically studied. The hemicage structure of the metal complexes was characterized by 1H NMR, indicating a pure facial geometry, in contrast to their uncaged cousins with 8-hydroxyquinoline (Mq3) and 3-methyl-8-hydroxyquinoline (M(3Meq)3), which all exist only as the meridional form in fluid solutions at room temperature. The photoluminescence quantum efficiency for the three hemicage complexes is 1.48, 1.79, and 1.26 times higher for AlQ, GaQ, and InQ, respectively, than their corresponding 3-methyl-8-hydroxyquinoline complexes, likely due to the rigidity of the ligand system, which can efficiently decrease the nonradiative decay of the excited states. The improved electrochemical stability of the hemicage complexes has been demonstrated by cyclic voltammetry, showing an increasingly reversible behavior from InQ to GaQ to AlQ (Ered=-2.15, -2.17, and -2.22 V vs Fc/Fc+ in DMSO). We infer that the degree of reversibility and redox potential result from the metal-ligand bond strength, which is largest in the case of aluminum.

Controlling the helicity of 2,2'-bipyridyl ruthenium(II) and zinc(II) hemicage complexes.

Two enantiomers of a new 4,5-pineno-2,2'-bipyridine ligand were synthesized and subsequently incorporated into hemicage ligands through a phenyl linker to yield ligands (+)-L1 and (-)-L1 or through a mesityl linker to yield ligands (+)-L2 and (-)-L2. Complexation of these ligands to Ru(II) afforded diastereomerically pure Delta and Lambda isomers, as verified through circular dichroism and circularly polarized luminescence spectroscopy. Ligands (+)-L2 and (-)-L2 were further coordinated to Zn(II) to form a complex with intriguing photophysical properties. Whereas Zn(bpy)32+ was shown to be a fluorescent emitter outside the visible spectrum, the caging process provided an unprecedented enhancement of intersystem crossing and subsequent switching to the phosphorescent emission of blue light. Additionally, the chiroptical properties of the Zn(II) complexes were also studied.