Computational Mechanistic Insights on the NO Oxidation Reaction Catalyzed by Non-Heme Biomimetic Cr-N-Tetramethylated Cyclam Complexes

The conversion reaction of NO to NO3− ion catalyzed by the end-on [Cr(III)(n-TMC)(O2)(Cl)]+ superoxo and side-on [Cr(IV)(n-TMC)(O2)(Cl)]+ peroxo non-heme complexes (n = 12, 13, 14 and 15), which are biomimetic systems of nitric oxide dioxygenases (NODs), has been explored using a computational protocol in the framework of density functional theory. Results show that the potential energy profiles for the studied reactions lie above the reagent energies, regardless of the used catalyst. Both the O-O bond breaking in the biomimetics and the NO3− ion formation require low energy barriers suggesting an efficient catalytic power of the studied systems. The rate-determining step depends on ligand size.

Toward Advanced Functional Systems: Honeycomb-Like Polymeric Surfaces Incorporating Polyoxovanadates with Surface-Appended Copper-Cyclam Complexes

In this work the immobilization of hybrid polyoxometalates (POMs) onto functional polymeric surfaces is exposed and discussed. Thus, various hybrid polymer‒inorganic films were prepared by anchoring selected hybrid POMs onto tailored polymeric surfaces that consisted of breath figures (BFs) made of polystyrene-b-poly(acrylic acid)/polystyrene (PS-b-PAA/PS) blends. Functionalization of the BF films was performed by selective arrangement of acrylic acid groups of the amphiphilic block copolymer on the surface pores because of their affinition for the water condensed during breath figure formation. These carboxylic acid functional groups contained within the PAA blocks were then employed to anchor [Cu(cyclam)][{Cu(cyclam)}2(V10O28)]·10H2O (1-CuV10) and [{Cu(cyclam)}(VO3)2]·5H2O (1-CuV1), hybrid POMs by immersing the films into aqueous solutions of the in situ formed hybrid clusters, resulting in the hybrid films BF1 and BF2, respectively. Superficial analysis of these hybrid polymeric films was carried out by the sophisticated ion beam-based technique time-of-flight secondary ion mass spectrometry (ToF-SIMS) that was revealed to be an excellent method for the superficial compositional mapping of patterned surfaces.

Sulfur substitution in a Ni(cyclam) derivative results in lower overpotential for CO2 reduction and enhanced proton reduction

N/S replacement in Ni-cyclam complexes highlights the importance of biologically relevant sulfur ligands in the CO2 and proton reduction.

Electrochemical [11C]CO2to [11C]CO conversion for PET imaging

Development of a novel electrochemical radiochemistry methodologyi.e.reduction of [11C]CO2to [11C]CO at room temperature and pressure using metal cyclam complexes.

Carbon neutral electrochemical conversion of carbon dioxide mediated by [Mn+(cyclam)Cln] (M = Ni2+ and Co3+) on mercury free electrodes and ionic liquids as reaction media

Carbon dioxide is reduced to carbon monoxide with high faradaic efficiency on mercury free electrodes using M(cyclam) complexes.