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null (Ed.)Through a combination of many analytical approaches, we show that a metal organic nanotube (UMON) displays selectivity for H 2 O over all types of heavy water (D 2 O, HDO, HTO). Water adsorption experiments combined with vibrational and radiochemical analyses reveal significant differences in uptake and suggest that surface adsorption processes may be a key driver in water uptake for this material.more » « less
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Fetrow, Taylor V.; Zgrabik, Joshua; Bhowmick, Rina; Eckstrom, Francesca D.; Crull, George; Vlaisavljevich, Bess; Daly, Scott R. (, Angewandte Chemie International Edition)Abstract Qualitative differences in the reactivity of trivalent lanthanide and actinide complexes have long been attributed to differences in covalent metal‐ligand bonding, but there are few examples where thermodynamic aspects of this relationship have been quantified, especially with U3+and in the absence of competing variables. Here we report a series of dimeric phosphinodiboranate complexes with trivalentf‐metals that show how shorter‐than‐expected U−B distances indicative of increased covalency give rise to measurable differences in solution deoligomerization reactivity when compared to isostructural complexes with similarly sized lanthanides. These results, which are in excellent agreement with supporting DFT and QTAIM calculations, afford rare experimental evidence concerning the measured effect of variations in metal‐ligand covalency on the reactivity of trivalent uranium and lanthanide complexes.more » « less
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