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Side-on Coordination in Isostructural Nitrous Oxide and Carbon Dioxide Complexes of Nickel.

ABSTRACT: A nickel complex incorporating an N₂ O ligand with a rare η² -N,N'-coordination mode was isolated and characterized by X-ray crystallography, as well as by IR and solid-state NMR spectroscopy augmented by ¹⁵ N-labeling experiments. The isoelectronic nickel CO₂ complex reported for comparison features a very similar solid-state structure. Computational studies revealed that η² -N₂ O binds to nickel slightly stronger than η² -CO₂ in this case, and comparably to or slightly stronger than η² -CO₂ to transition metals in general. Comparable transition-state energies for the formation of isomeric η² -N,N'- and η² -N,O-complexes, and a negligible activation barrier for the decomposition of the latter likely account for the limited stability of the N₂ O complex.

SUBMITTER: Puerta Lombardi BM

PROVIDER: S-EPMC8048599 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Solvent-assisted ligand incorporation (SALI) of the ditopic linker 5-carboxy-3-(4-carboxybenzyl)thiazolium bromide [(H2PhTz)Br] into the zirconium metal-organic framework NU-1000 [Zr6O4(OH)8(H2O)4(TBAPy)2, where NU = Northwestern University and H4TBAPy = 1,3,6,8-tetrakis(p-benzoic-acid)pyrene], led to the SALIed NU-1000-PhTz material of minimal formula [Zr6O4(OH)6(H2O)2(TBAPy)2(PhTz)]Br. NU-1000-PhTz has been thoroughly characterized in the solid state. As confirmed by powder X-ray diffraction, this material keeps the same three-dimensional architecture of NU-1000 and the dicarboxylic extra linker bridges adjacent [Zr6] nodes ca. 8 Å far apart along the crystallographic c-axis. The functionalized MOF has a BET specific surface area of 1560 m2/g, and it is featured by a slightly higher thermal stability than its parent material (Tdec = 820 vs. 800 K, respectively). NU-1000-PhTz has been exploited for the capture and separation of two pollutant gases: carbon dioxide (CO2) and nitrous oxide (N2O). The high thermodynamic affinity for both gases [isosteric heat of adsorption (Qst) = 25 and 27 kJ mol-1 for CO2 and N2O, respectively] reasonably stems from the strong interactions between these (polar) "stick-like" molecules and the ionic framework. Intriguingly, NU-1000-PhTz shows an unprecedented temperature-dependent adsorption capacity, loading more N2O in the 298 K ≤ T ≤ 313 K range but more CO2 at temperatures falling out of this range. Grand canonical Monte Carlo simulations of the adsorption isotherms confirmed that the preferential adsorption sites of both gases are the triangular channels (micropores) in close proximity to the polar pillar. While CO2 interacts with the thiazolium ring in an "end-on" fashion through its O atoms, N2O adopts a "side-on" configuration through its three atoms simultaneously. These findings open new horizons in the discovery of functional materials that may discriminate between polluting gases through selective adsorption at different temperatures.

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Side-on Coordination in Isostructural Nitrous Oxide and Carbon Dioxide Complexes of Nickel.

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