Metal–organic frameworks (MOFs) have high potential
as nanoplatforms
for the storage and delivery of therapeutic gasotransmitters or gas-releasing
molecules. The aim of the present study was to open an investigation
into the viability of tricarbonyl-pyrazine-molybdenum(0) MOFs as carbon
monoxide-releasing materials (CORMAs). A previous investigation found
that the reaction of Mo(CO)6 with excess pyrazine (pyz)
in a sealed ampoule gave a mixture comprising a major triclinic phase
with pyz-occupied hexagonal channels, formulated as fac-Mo(CO)3(pyz)3/2·1/2pyz (Mo-hex), and a minor dense cubic phase, formulated as fac-Mo(CO)3(pyz)3/2 (Mo-cub). In
the present work, an open reflux method in toluene has been optimized
for the large-scale synthesis of the pure Mo-cub phase.
The crystalline solids Mo-hex and Mo-cub were characterized by powder X-ray diffraction (PXRD), scanning
electron microscopy (SEM), thermogravimetric analysis (TGA), FT-IR
and FT-Raman spectroscopies, and 13C{1H} cross-polarization
(CP) magic-angle spinning (MAS) NMR spectroscopy. The release of CO
from the MOFs was studied by the deoxy-myoglobin (deoxy-Mb)/carbonmonoxy-myoglobin
(MbCO) UV–vis assay. Mo-hex and Mo-cub release CO upon contact with a physiological buffer in the dark,
delivering 0.35 and 0.22 equiv (based on Mo), respectively, after
24 h, with half-lives of 3–4 h. Both materials display high
photostability such that the CO-releasing kinetics is not affected
by irradiation of the materials with UV light. These materials are
attractive as potential CORMAs due to the slow release of a high CO
payload. In the solid-state and under open air, Mo-cub underwent almost complete decarbonylation over a period of 4 days,
corresponding to a theoretical CO release of 10 mmol per gram of material.