Two-dimensional, conductive niobium and molybdenum metal–organic frameworks
Michael E. Ziebel, Justin C. Ondry, Jeffrey R. Long
Abstract
X-ray absorption spectroscopy suggests a local trigonal prismatic coordination geometry for both niobium and molybdenum, consistent with their increased covalency relative to related first-row transition metal compounds. A combination of vibrational spectroscopy, magnetic susceptibility, and electronic conductivity measurements reveal that these two frameworks possess distinct electronic structures. In particular, while the niobium compound displays evidence for redox-trapping and strong magnetic interactions, the molybdenum phase is valence-delocalized with evidence of large polaron formation. Weak interlayer interactions in the neutral molybdenum phase enable solvent-assisted exfoliation to yield few-layer hexagonal nanosheets. Together, these results represent the first syntheses of metal-organic frameworks containing mononuclear niobium and molybdenum nodes, establishing a route to frameworks incorporating a more diverse range of second- and third-row transition metals with increased covalency and the potential for improved charge transport and stronger magnetic coupling.