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Title: Crystallographic characterization of the metal–organic framework Fe 2 (bdp) 3 upon reductive cation insertion

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/D0SC03383A· OSTI ID:1648159
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Department of Chemistry, University of California, Berkeley, USA, Materials Sciences Division
  2. Department of Chemistry, University of California, Berkeley, USA
  3. Department of Chemistry, University of California, Berkeley, USA, Department of Chemical and Biomolecular Engineering
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Precisely locating extra-framework cations in anionic metal–organic framework compounds remains a long-standing, yet crucial, challenge for elucidating structure–performance relationships in functional materials. Single-crystal X-ray diffraction is one of the most powerful approaches for this task, but single crystals of frameworks often degrade when subjected to post-synthetic metalation or reduction. Here, we demonstrate the growth of sizable single crystals of the robust metal–organic framework Fe2(bdp)3 (bdp2- = benzene-1,4-dipyrazolate) and employ single-crystal-to-single-crystal chemical reductions to access the solvated framework materials A2Fe2(bdp)3·yTHF (A = Li+, Na+, K+). X-ray diffraction analysis of the sodium and potassium congeners reveals that the cations are located near the center of the triangular framework channels and are stabilized by weak cation–π interactions with the framework ligands. Freeze-drying with benzene enables isolation of activated single crystals of Na0.5Fe2(bdp)3 and Li2Fe2(bdp)3 and the first structural characterization of activated metal–organic frameworks wherein extra-framework alkali metal cations are also structurally located. Comparison of the solvated and activated sodium-containing structures reveals that the cation positions differ in the two materials, likely due to cation migration that occurs upon solvent removal to maximize stabilizing cation–π interactions. Hydrogen adsorption data indicate that these cation–framework interactions are sufficient to diminish the effective cationic charge, leading to little or no enhancement in gas uptake relative to Fe2(bdp)3. In contrast, Mg0.85Fe2(bdp)3 exhibits enhanced H2 affinity and capacity over the non-reduced parent material. This observation shows that increasing the charge density of the pore-residing cation serves to compensate for charge dampening effects resulting from cation–framework interactions and thereby promotes stronger cation–H2 interactions.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; AC02-06CH11357
OSTI ID:
1648159
Alternate ID(s):
OSTI ID: 1756379
Journal Information:
Chemical Science, Journal Name: Chemical Science Vol. 11 Journal Issue: 34; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United Kingdom
Language:
English
Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY