{The complex {[}Ph4P](2){[}Cu(bdt)(2)] (1(red)) was synthesized by the reaction of {[}Ph4P]2{[}S2MoS2CuCl] with H2bdt (bdt = benzene-1,2-dithiolate) in basic medium. 1(red) is highly susceptible toward dioxygen, affording the one electron oxidized diamagnetic compound {[}Ph4P]{[}Cu(bdt)(2)] (1(ox)). The interconversion between these two oxidation states can be switched by addition of O-2 or base (Et4NOH = tetraethylammonium hydroxide), as demonstrated by cyclic voltammetry and UV-visible and EPR spectroscopies. Thiomolybdates, in free or complex forms with copper ions, play an important role in the stability of 1(red) during its synthesis, since in its absence, 1(ox) is isolated. Both 1(red) and 1(ox) were structurally characterized by X-ray crystallography. EPR experiments showed that 1(red) is a Cu(II)-sulfur complex and revealed strong covalency on the copper-sulfur bonds. DFT calculations confirmed the spin density delocalization over the four sulfur atoms (76%) and copper (24%) atom, suggesting that 1(red) has a ``thiyl radical character{''}. Time dependent DFT calculations identified such ligand to ligand charge transfer transitions. Accordingly, 1(red) is better described by the two isoelectronic structures {[}Cu(I)(bdt(2), 4S(3-{*}))](2-) {[}Cu-II(bdt(2), 4S(4-))](2-). On thermodynamic grounds, oxidation of 1(red) (doublet state) leads to 1(ox) singlet state, {[}Cu-III(bd(t)2, 4S(4-))](1-).}

N2OR has been found to have two structural forms of its tetranuclear copper active site, the 4CuS Cu(Z)* form and the 4Cu2S Cu(Z) form. EPR, resonance Raman, and MCD spectroscopies have been used to determine the redox states of these sites under different reductant conditions, showing that the Cu(Z)* site accesses the 1-hole and fully reduced redox states, while the Cu(Z) site accesses the 2-hole and 1-hole redox states. Single-turnover reactions of N2OR for Cu(Z) and Cu(Z)* poised in these redox states and steady-state turnover assays with different proportions of Cu(Z) and Cu(Z)* show that only fully reduced Cu(Z)* is catalytically competent in rapid turnover with N2O.

n/a

A novel immobilized Ca0.6Ho0.4MnO3 photocatalyst has been developed with high photocatalytic activity for Rhodamine 6G (Rh6G) photodegradation under visible light irradiation. The nanocrystalline Ca0.6Ho0.4MnO3 films were successfully deposited by RF-magnetron sputtering on unheated quartz glass substrates using Ca0.6Ho0.4MnO3 powder as sputtering target and its photocatalytic functionalities have been explored. The visible-light-responsive photocatalytic activity of Ca0.6Ho0.4MnO3 films was evaluated by the photodegradation of Rh6G aqueous solutions under visible light irradiation. The reusability of Ca0.6Ho0.4MnO3 films on fresh dye samples was studied, showing an efficient reuse, without decreasing the photocatalytic decolorization efficiency. Furthermore, X-ray diffraction of the reused films did not reveal additional phases indicating high photochemical stability of the films even after reusing them in successive runs. The photocatalytic efficiency of the nanocrystalline Ca0.6Ho0.4MnO3 films was further compared with TiO2 films also produced by sputtering and the results revealed a significant improvement in photocatalytic activity over TiO2 under visible light irradiation. Almost complete photodecolorization of a 5 ppm Rh6G solution was achieved in 4 h, while only 64% of dye degradation was observed in TiO2 photoassisted process. This work provides a feasible route to fabricate high-performance immobilized ABO3-based nanomaterials, and the finding opens up a new venue for designing visible light sensitive ternary compounds for photocatalytical applications. A novel immobilized Ca0.6Ho0.4MnO3 photocatalyst has been developed with high photocatalytic activity for Rhodamine 6G (Rh6G) photodegradation under visible light irradiation. The nanocrystalline Ca0.6Ho0.4MnO3 films were successfully deposited by RF-magnetron sputtering on unheated quartz glass substrates using Ca0.6Ho0.4MnO3 powder as sputtering target and its photocatalytic functionalities have been explored. The visible-light-responsive photocatalytic activity of Ca0.6Ho0.4MnO3 films was evaluated by the photodegradation of Rh6G aqueous solutions under visible light irradiation. The reusability of Ca0.6Ho0.4MnO3 films on fresh dye samples was studied, showing an efficient reuse, without decreasing the photocatalytic decolorization efficiency. Furthermore, X-ray diffraction of the reused films did not reveal additional phases indicating high photochemical stability of the films even after reusing them in successive runs. The photocatalytic efficiency of the nanocrystalline Ca0.6Ho0.4MnO3 films was further compared with TiO2 films also produced by sputtering and the results revealed a significant improvement in photocatalytic activity over TiO2 under visible light irradiation. Almost complete photodecolorization of a 5 ppm Rh6G solution was achieved in 4 h, while only 64% of dye degradation was observed in TiO2 photoassisted process. This work provides a feasible route to fabricate high-performance immobilized ABO3-based nanomaterials, and the finding opens up a new venue for designing visible light sensitive ternary compounds for photocatalytical applications.

The complex [Ph4P]2[Cu(bdt)2] (1(red)) was synthesized by the reaction of [Ph4P]2[S2MoS2CuCl] with H2bdt (bdt = benzene-1,2-dithiolate) in basic medium. 1(red) is highly susceptible toward dioxygen, affording the one electron oxidized diamagnetic compound [Ph4P][Cu(bdt)2] (1(ox)). The interconversion between these two oxidation states can be switched by addition of O2 or base (Et4NOH = tetraethylammonium hydroxide), as demonstrated by cyclic voltammetry and UV-visible and EPR spectroscopies. Thiomolybdates, in free or complex forms with copper ions, play an important role in the stability of 1(red) during its synthesis, since in its absence, 1(ox) is isolated. Both 1(red) and 1(ox) were structurally characterized by X-ray crystallography. EPR experiments showed that 1(red) is a Cu(II)-sulfur complex and revealed strong covalency on the copper-sulfur bonds. DFT calculations confirmed the spin density delocalization over the four sulfur atoms (76%) and copper (24%) atom, suggesting that 1(red) has a "thiyl radical character". Time dependent DFT calculations identified such ligand to ligand charge transfer transitions. Accordingly, 1(red) is better described by the two isoelectronic structures [Cu(I)(bdt2, 4S(3-,)*)](2-) <--> [Cu(II)(bdt2, 4S(4-))](2-). On thermodynamic grounds, oxidation of 1(red) (doublet state) leads to 1(ox) singlet state, [Cu(III)(bdt2, 4S(4-))](1-).

Ca1-xSmxMnO3 (0≤x≤0.4) films were successfully fabricated on Indium Tin Oxide (ITO) coated quartz glass substrates by radio frequency magnetron sputtering technique (RF- magnetron sputtering) from compacted nanosized powder targets, and subsequent annealing at 800°C in air, for 6h. X-ray diffraction shows a pure typical perovskite phase for x≥0.1. Scanning electron microscopy and atomic force microscopy revealed that the film surface is dense, with low roughness, depending on the Sm content, even though a few cracks were observed. Crystallite size was found to decrease with the Sm content. The electrodes were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS).The oxide electrode's capacitance was estimated using both techniques and the corresponding roughness factors evaluated. The values obtained from the two methods show a good agreement. A comparison between the voltammetric data and those referred in the literature allowed finding out that the redox reaction occurring at the electrode surface involves the pair Mn4+/Mn3+. EIS measurements confirm the voltammetric data and they also give additional information about the film porosity and the charge transfer resistance. This last parameter is associated with the oxidation and reduction of the pair Mn3+/Mn4+and after normalized by the roughness factor shows an increase with samarium content.