Confinement of bulk materials to nanoparticles and molecular clusters results in emergent, size dependent phenomena including enhanced magnetic susceptibility and superparamagnetism. Upon confinement to particles of only tens of atoms, these properties become highly sensitive to slight changes in particle size and geometry. While synthetic advances in transition metal carbonyl chemistry have led to a diverse library of clusters for various transition metals, fine control over cluster geometry remains elusive. In this work, metal–organic frameworks are explored as templates for the controlled growth of molecular clusters. Metal–organic frameworks are porous, three-dimensional coordination solids assembled from inorganic nodes and organic linkers. It is anticipated that framework pores will be able to impart their geometries to clusters grown within the framework. Post-synthetic metallation of the framework Zr6O4(OH)4(bpydc)6 (bpydc = 2,2’-bipyridine-5,5’-dicarboxylate) with Fe(CO)5 and Fe(CO)2(NO)2 will be presented as well as preliminary results on the growth of iron clusters.

Metal–organic frameworks as templates for transition metal clusters

253rd National Meeting (2017)

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