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Turner, David R.
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article
Ultramicroporous MOF with high concentration of vacant CuII sites
Abstract
<p>An ultramicroporous metal-organic framework (MOF) is reported that contains 0.35 nm nanotube-like channels with an unprecedented concentration of vacant Cu<sup>II</sup> coordination sites. The nonintersecting, narrow channels in [Cu<sub>3</sub>(cdm)<sub>4</sub>] (cdm = C(CN)<sub>2</sub>(CONH<sub>2</sub>)<sup>-</sup>) align in two perpendicular directions, structurally resembling copper-doped carbon nanotubes with Cu<sup>II</sup> embedded in the walls of the channels. The combination of ultramicroporosity with the exposed Cu<sup>II</sup> coordination sites gives size-based selectivity of CO<sub>2</sub> over CH<sub>4</sub>, based on pore-size distribution and modeling. Neutron powder diffraction and molecular dynamics simulations show the close packing of single rows of guests within the tubular nanostructure and interaction of CO<sub>2</sub> with the exposed metal sites.</p>