Enhanced electrical properties of amorphous In-Sn-Zn oxides through heterostructuring with BiSe topological insulators.

Amorphous indium tin zinc oxide (a-ITZO)/BiSe nanoplatelets (NPs) were fabricated using a two-step procedure. First, BiSe NPs were synthesized through thermal chemical vapor deposition at 600 °C on a glass substrate, and then a-ITZO was deposited on the surface of the BiSe NPs via magnetron sputtering at room-temperature. The crystal structures of the a-ITZO/BiSe NPs were determined via X-ray diffraction spectroscopy and high-resolution transmission electron microscopy.

Shape Dependence of Silver-Nanoparticle-Mediated Synthesis of Gold Nanoclusters with Small Molecules as Capping Ligands.

In this study, differently shaped silver nanoparticles used for the synthesis of gold nanoclusters with small capping ligands were demonstrated. Silver nanoparticles provide a reaction platform that plays dual roles in the formation of Au NCs. One is to reduce gold ions and the other is to attract capping ligands to the surface of nanoparticles.

Silver Nanoparticle-Mediated Synthesis of Fluorescent Thiolated Gold Nanoclusters.

A new strategy using silver nanoparticles (Ag NPs) to synthesize thiolated Au NCs is demonstrated. The quasi-spherical Ag NPs serve as a platform, functioning as a reducing agent for Au (III) and attracting capping ligands to the surface of the Ag NPs. Glutathione disulfide (GSSG) and dithiothreitol (DTT) were used as capping ligands to synthesize thiolated Au NCs (glutathione-Au NCs and DTT-Au NCs).

Assessment of the intramolecular magnetic interactions in the highly saddled iron(iii) porphyrin π-radical cations: the change from planar to saddle conformations.

The intramolecular magnetic interactions in one-electron oxidized iron(iii) porphyrin π-radical cations, [Fe(OETPP˙)Cl][SbCl6] (1), [Fe(OMTPP˙)Cl][SbCl6] (2) and [Fe(TPP˙)Cl][SbCl6] (3), have been compared by means of X-ray crystallography, SQUID magnetometry, cyclic voltammetry, UV-Vis spectroelectrochemical analysis, NMR spectroscopy analysis and unrestricted DFT calculations. Unlike a generally recognized antiferromagnetic coupling dxy↑dxz↑dyz↑dz2↑dx2-y2↑P˙+(a2u)↓ (S = 2) state via a weak bonding interaction as in (3), we have disclosed that a strong bonding interaction among iron dx2-y2 and porphyrin a2u orbitals forms in (1) into a highly delocalized Ψπ = [P˙+(a2u) + FeIII(dx2-y2, dz2)] orbital that is able to accommodate two spin-paired electrons to form the Ψπ2dxy1dxz1dyz1, dz21 (S = 2) ground state. Concurrently, the spin polarization effect is exerted on the paired spins in the Ψπ orbital by magnetic induction from the remaining unpaired electrons in the iron d orbitals.

A Mn(iv)-peroxo complex in the reactions with proton donors.

Protons play an important role in promoting O-O or M-O bond cleavage of metal-peroxo complexes. Treatment of side-on O2-bound [PPN][MnIV(TMSPS3)(O2)] (1, PPN = bis(triphenylphosphine)iminium and TMSPS3H3 = 2,2',2''-trimercapto-3,3',3''-tris(trimethylsilyl)triphenylphosphine) with perchloric acid (HClO4) in the presence of PR3 (R = phenyl or p-tolyl) results in the formation of neutral five-coordinate MnIII(OPR3)(TMSPS3) complexes (R = phenyl, 2a; p-tolyl, 2b), which are confirmed by X-ray crystallography. Isotope labelling experiments demonstrate that the oxygen atom in the phosphine oxide product derives from the peroxo ligand of 1.

A Switch from Mechanistic Competition Mediated by a Combination of Temperature and Concentration Effects in the Oxidation Reaction of [Fe (N4Py/TPA)](OTf).

The formation of [(N4Py)Fe =O] species was accomplished by the reaction of [Fe (N4Py)] with 20 equivalents of tBuO H (TBHP, 70 % in H O). The temperature, [Fe (N4Py)] -concentration and H O-concentration in anhydrous TBHP (5.5 m in decane) dependences of its yields and rates were analyzed to indicate that the proton migration from [(N4Py)Fe -HOOtBu] to [(N4Py)Fe -OO HtBu] is the rate-determining step followed by rapid heterolytic O-O bond cleavage of Fe -OO HtBu to Fe =O complex.

The characterization of the saddle shaped nickel(III) porphyrin radical cation: an explicative NMR model for a ferromagnetically coupled metallo-porphyrin radical.

Ni(III)(OETPP˙)(Br)2 is the first Ni(III) porphyrin radical cation with structural and (1)H and (13)C paramagnetic NMR data for porphyrinate systems. Associating EPR and NMR analyses with DFT calculations as a new model is capable of clearly determining the dominant state from two controversial spin distributions in the ring to be the Ni(III) LS coupled with an a1u spin-up radical.