Electrophotocatalytic perfluoroalkylation by LMCT excitation of Ag(II) perfluoroalkyl carboxylates.

Molecular Ag(II) complexes are superoxidizing photoredox catalysts capable of generating radicals from redox-reticent substrates. In this work, we exploited the electrophilicity of Ag(II) centers in [Ag(bpy)(TFA)][OTf] and Ag(bpy)(TFA) (bpy, 2,2'-bipyridine; OTf, CFSO) complexes to activate trifluoroacetate (TFA) by visible light-induced homolysis. The resulting trifluoromethyl radicals may react with a variety of arenes to forge C(sp)-CF bonds.

Lewis Acid Supported Nickel Nitrenoids.

Metalation of the polynucleating ligand LH (1,3,5-C H (NC H -4-F-2-NSiMe Bu) ) with two equivalents of Zn(N(SiMe ) ) affords the dinuclear product ( LH )Zn (1), which can be further deprotonated to yield ( L)Zn Li (OEt ) (2). Transmetalation of 2 with NiCl (py) yields the heterometallic, trinuclear cluster ( L)Zn Ni(py) (3). Reduction of 3 with KC affords [KC ][( L)Zn Ni] (4) which features a monovalent Ni centre.

Light-Mediated Electrochemical Synthesis of Manganese Oxide Enhances Its Stability for Water Oxidation.

New methods are needed to increase the activity and stability of earth-abundant catalysts for electrochemical water splitting to produce hydrogen fuel. Electrodeposition has been previously used to synthesize manganese oxide films with a high degree of disorder and a mixture of oxidation states for Mn, which has led to electrocatalysts with high activity but low stability for the oxygen evolution reaction (OER) at high current densities. In this study, we show that multipotential electrodeposition of manganese oxide under illumination produces nanostructured films with significantly higher stability for the OER compared to films grown under otherwise identical conditions in the dark.

Crystal structure of a methyl benzoate quadruple-bonded dimolybdenum complex.

Quadruple-bond dimolybdenum complexes provide invaluable insight into the two-electron bond, with structural chemistry providing a foundation for examination of bond properties. The synthesis and solid-state structure of the quadruple-bonded dimolybdenum(II) complex tetra-kis-(-4-methyl-benzoato- :')bis[(tetra-hydro-furan-κ)molybdenum(II)] tetra-hydro-furan disolvate, [Mo(CHO)(CHO)]·2CHO, are presented. This complex crystallizes in a triclinic cell with low-symmetry space group .

Spontaneous Seed Formation during Electrodeposition Drives Epitaxial Growth of Metastable Bismuth Selenide Microcrystals.

Materials with metastable phases can exhibit vastly different properties from their thermodynamically favored counterparts. Methods to synthesize metastable phases without the need for high-temperature or high-pressure conditions would facilitate their widespread use. We report on the electrochemical growth of microcrystals of bismuth selenide, BiSe, in the metastable orthorhombic phase at room temperature in aqueous solution.

Probing the Halide Effect in the δ-Bond with One- and Two-Photon Spectroscopy.

Two electrons in two orbitals give rise to four states. When the orbitals are weakly coupled as in the case for the d orbitals of quadruple bond species, two of the states are diradical in character with electrons residing in separate orbitals and two of the states are zwitterionic with electrons paired in one orbital or the other. By measuring one-and two-photon spectra, the one-electron (ΔW) and two-electron (K) energies may be calculated, which are the determinants of the state energies of the four-state model for the two-electron bond.