New topological 3D copper(ii) coordination networks: catechol oxidation catalysis and solvent adsorption via porous properties

Abstract

The reaction of CuX₂ (X⁻ = ClO₄⁻ and BF₄⁻) with a new 1,3,5-tris(isonicotinoyloxymethyl)benzene (L) ligand gives rise to 3D coordination networks, [Cu₃L₄(CH₃CN)₆](X)₆, with a new topology of the Schläfli point symbol {4·8²}₄{4²·8²·10²}₂{8⁴·12²}. [Cu₃L₄(CH₃CN)₆](ClO₄)₆ and [Cu₃L₄(CH₃CN)₆](BF₄)₆ networks have useful oval-shaped pores of 11.2 × 11.2 × 24.8 ų and 11.1 × 11.1 × 24.4 ų dimensions, respectively. These porous coordination networks act as good heterogeneous catalysts, oxidizing the catechols in the order 3,5-di-tert-butylcatechol (3,5-DBuCat) > 4-tert-butylcatechol (4-BuCat) > 4-chlorocatechol (4-ClCat). The catalytic effect of [Cu₃L₄(CH₃CN)₆](BF₄)₆ is slightly higher than that of [Cu₃L₄(CH₃CN)₆](ClO₄)₆. The pores of the 3D networks reversibly adsorb the solvents in the order chloroform > tetrahydrofuran > acetone.