Nano-architecture of silica nanoparticles as a tool to tune both electrochemical and catalytic behavior of NiII@SiO2.

The present work introduces a facile synthetic route for efficient doping of [NiII(bpy) x ] into silica nanoparticles with various sizes and architectures. Variation of the latter results in different concentrations of the NiII complexes at the interface of the composite nanoparticles. The UV-Vis analysis of the nanoparticles reveals changes in the inner-sphere environment of the NiII complexes when embedded into the nanoparticles, while the inner-sphere of NiII is invariant for the nanoparticles with different architecture. Comparative analysis of the electrochemically generated redox transformations of the NiII complexes embedded in the nanoparticles of various architectures reveals the latter as the main factor controlling the accessibility of NiII complexes to the redox transitions which, in turn, controls the electrochemical behavior of the nanoparticles. The work also highlights an impact of the nanoparticulate architecture in catalytic activity of the NiII complexes within the different nanoparticles in oxidative C-H fluoroalkylation of caffeine. Both low leakage and high concentration of the NiII complexes at the interface of the composite nanoparticles enables fluoroalkylated caffeine to be obtained in high yields under recycling of the nanocatalyst five times at least.

Nanoheterogeneous catalysis in electrochemically induced olefin perfluoroalkylation.

Ni-catalyzed electroreductive olefin perfluoroalkylation affords both monomeric and dimeric products depending on the reaction media. Recycling of the catalyst can be achieved by immobilization of a (bpy)NiBr2 complex on silica nanoparticles decorated with anchoring amino-groups. Switching the homogeneous and heterogeneous catalysts is found to be one more factor to control the product ratio. This catalytic technique is both green and atom economical and combines the advantages of nanoheterogeneous catalysis and electrocatalysis.

New NIR-emissive tetranuclear Er(III) complexes with 4-hydroxo-2,1,3-benzothiadiazolate and dibenzoylmethanide ligands: synthesis and characterization.

New tetranuclear heteroleptic complexes [Er4(dbm)6(O-btd)4(OH)2] (1) and [Er4(dbm)4(O-btd)6(OH)2] (2) (O-btd = 4-hydroxo-2,1,3-benzothiadiazolate and dbm = dibenzoylmethanide) and their solvates with toluene, THF and CH2Cl2 were prepared using two synthetic approaches. The structures of the products were confirmed by single-crystal X-ray diffraction. Magnetic properties of 1 and 2 are in good agreement with X-ray data. The effective magnetic moment (µeff) values at 300 K for 1 and 2 corresponds to a system of 4 non-interacting Er(III) ions in the ground state 4J15/2 with g = 6/5. At ambient temperature and upon excitation with λexc = 450 nm, complexes 1 and 2 exhibit luminescence at 1530 nm, i.e. in the near infra-red (NIR) region. The luminescence intensity grows with increasing the number of the (O-btd)− ligands in the complexes. This observation suggests (O-btd)− as a new efficient antenna ligand for the lanthanide-based NIR luminescence.