RESUMO
Two 1D coordination polymers (CPs) with general formula [M(L)(H2O)(AcO)]n, (M = Co (1) or Cd (2), AcO = acetate anion and L denotes l-phenylalanine based ligand), were synthesized and fully characterized by various spectroscopies (UV-vis, FTIR, and NMR), thermal techniques, magnetic measurements (for 1), and single-crystal and powder X-ray diffraction studies. They can be described as "ribbon-like" 1D polymers constructed through a zigzag arrangement. The polymeric structure is developed due to the coordination mode adopted by the amino acid ligand, classified as µ3-N1O1:O1:O2, which simultaneously links three metal centers. This moiety also plays an important role as a magnetic coupler between metal centers in the cobalt system, which shows a weak antiferromagnetic interaction. Both CPs have also been used in the catalytic oxidation of cyclohexene with molecular oxygen (O2) as an oxidant. Under mild conditions, both compounds demonstrated remarkable catalytic activity, with the cobalt system being more efficient than the cadmium analogue (conversion: 73 and 58% and selectivity for the major product, 2-cyclohexanone: 63 and 55%, for 1 and 2, respectively). Leaching experiments and the results obtained using a radical quencher are consistent with a radical-mediated mechanism for the Co compound. The presence of the superoxide radical was also confirmed using EPR spectroscopy and DMPO as a spin trap, which was further validated by DFT calculations. The activity observed for the Cd analogue is attributed to the organic scaffold assisted by the templating effect of the metal ion.
RESUMO
Vanadium oxides present a rich magnetic phase diagram depending on the oxidation state of the V ions. In particular the vanadium oxide nanotubes (VO x NTs) present several promising perspectives for different technological applications for which it is essential to know the oxidation state of V ions, as well as to evaluate the stability with the aging time of the tubes. In this work we present a systematic study of the time evolution of the magnetic properties of VO x NTs. For this complete characterization, we used electron spin resonance (ESR) and dc-susceptibility techniques, which were supplemented with TEM microscopy and XANES. We observed that for aging in normal environmental conditions of pressure, temperature and humidity, the V4+ ions oxidize to V5+ . Although the multiwall tubular structure is maintained, this oxidation process produces a marked change in the magnetic properties. We conclude that the aging of the samples affects the V4+ /V5+ relationship in the VO x NTs, which may contribute to explain the significant dispersion of data reported in the bibliography.