Two new copper(ii) polymeric complexes, [Cu(HPymat)(H 2 O)](NO 3 ) n (1) and [Cu 2 (Pymat) 2 (H 2 O) 3 ] n (2), have been synthesized using the Schiff base ligand H 2 Pymat [H 2 Pymat = (E)-2-(1-(pyridin-2-yl)-methyleneamino)terephthalic acid]. Complex 1 is a cationic 1D polymer, whereas complex 2 is a two dimensional polymer. Both complexes were crystallographically, spectroscopically and magnetically characterized. Theoretical studies were performed and the catecholase activity of the complexes was also examined. Complex 1 is a ferromagnetically coupled complex with J = 2.8 cm −1 and 2 shows antiferromagnetic coupling with J = −1.6 cm −1 . Both complexes show notable features in the EPR study. They show rhombic spectra at 77 K in the solid state, but by varying the temperature or solvents the nature of the spectra can be changed or inverted. This behaviour indicates a change of the ground state from d x 2 −y 2 to d z 2 orbitals. Theoretical calculations of 1 focus on the evaluation and characterization of interesting anion-π-anion assemblies that are formed in the solid state. In 2 we have analysed the unconventional chelate ring...chelate ring π-stacking interactions that govern its solid state architecture. Both complexes act as functional models and show catechol oxidase activity with a k cat value of the order of 10 3 h −1 .
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|Titolo:||Effect of temperature and ligand protonation on the electronic ground state in Cu(ii) polymers having unusual secondary interactions: a magnetic and catechol oxidase study|
|Data di pubblicazione:||2018|
|Appare nelle tipologie:||1.1 Articolo in rivista|