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One atom can make all the difference: Gas-induced phase transformations in bisimidazole-linked diamondoid coordination networks

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Coordination networks (CNs) that undergo gas-induced transformation from closed (nonporous) to open (porous) structures are of potential utility in gas storage applications, but their development is hindered by limited control over their switching mechanisms and pressures. In this work, we report two CNs, [Co(bimpy)(bdc)]n (X-dia-4-Co) and [Co(bimbz)(bdc)]n (X-dia-5-Co) (H2bdc = 1,4-benzendicarboxylic acid; bimpy = 2,5-bis(1H-imidazole-1-yl)pyridine; bimbz = 1,4-bis(1H-imidazole-1-yl)benzene), that both undergo transformation from closed to isostructural open phases involving at least a 27% increase in cell volume. Although X-dia-4-Co and X-dia-5-Co only differ from one another by one atom in their N-donor linkers (bimpy = pyridine, and bimbz = benzene), this results in different pore chemistry and switching mechanisms. Specifically, X-dia-4-Co exhibited a gradual phase transformation with a steady increase in the uptake when exposed to CO2, whereas X-dia-5-Co exhibited a sharp step (type F-IV isotherm) at P/P0 0.008 or P 3 bar (195 or 298 K, respectively). Single-crystal X-ray diffraction, in situ powder XRD, in situ IR, and modeling (density functional theory calculations, and canonical Monte Carlo simulations) studies provide insights into the nature of the switching mechanisms and enable attribution of pronounced differences in sorption properties to the changed pore chemistry.

Funding

Crystal Engineering of Task-Specific Materials

Science Foundation Ireland

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Green Adsorbents for Clean Energy (GrACE)

Science Foundation Ireland

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Kinetics and Thermodynamics of Gaseous Mixtures in Nano-Confined Environments

Office of Basic Energy Sciences

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AMBER_Phase 2

Science Foundation Ireland

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History

Publication

Journal of the American Chemical society, 2023, 145, pp. 10197-10207

Publisher

American Chemical Society

Also affiliated with

  • Bernal Institute

Department or School

  • Chemical Sciences

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