Synthesis and characterization of inorganic-organic hybrid materials based on the intercalation of stable organic radicals into a fluoromica clay

摘要

Hybrid materials, in which stable organic radical cations are intercalated into layered inorganic host materials, can be successfully synthesized via an ion exchange reaction in a layered fluoromica clay, to yield recyclable heterogeneous catalysts for oxidation of various alcohols. We have conducted systematic synthetic and structural studies on the intercalation of the radical cations 4-(diethylmethylammonium)-2,2,6,6-tetramethylpiperidin-1-oxyl (DEMTEP), 1-[2-(4-amino-2,2,6,6-tetramethyl-1-piperidinyloxyl)-2-oxoethyl] -1′-methyl-4,4′-bipyridinium (VIOTEP), and 2-(3-N-methylpyridinium)- 4,4,5,5-tetramethyl-4,5-dihydro-~1H-imidazol-1-oxyl-3-N-oxide (m-MPYNN) into a synthetic fluoromica clay named Somasif? ME 100, Na_(2x)Mg _(3.0-x)Si_4O_(10)(F_yOH_(1-y)) _2 (x = 0.33, y = 0.98). The guest-host interactions in these intercalation compounds have been characterized by X-ray powder diffraction and solid-state NMR of the constituent nuclei (~(23)Na, ~(19)F, and ~(29)Si) of the Somasif structure. The intercalation process can be conveniently monitored using ~(23)Na MAS-NMR. Guest-guest interactions have been probed by magnetic susceptibility measurements as well as EPR and ~1H MAS NMR experiments. The ~1H MAS-NMR line widths and chemical shifts probe modifications in the electron spin density distributions and/or intermolecular interactions between the electron spins of the guest species. Despite these indications of weakly interacting spins, magnetic susceptibility measurements are consistent with the near-absence of cooperative magnetism. The VIOTEP and DEMTEP inclusion compounds demonstrate catalytic activity for the oxidation of benzyl alcohol, using NaOCl as a co-oxidant. Although the radical ion species is partially leached out under these conditions (ionic exchange with Na~+ in solution) the catalytic activity remains for up to 40 subsequent cycles. Fully leached materials can be regenerated by catalyst re-loading and this process can be conveniently monitored by X-band EPR spectroscopy.