Constraining Flexibility in the MIL-88 Topology through Integration of 3-Dimensional Linkers

Smoljan, Courtney S.; Sha, Fanrui; Campitelli, Patrizio; Xie, Haomiao; Eddaoudi, Manel A.; Mian, Mohammad Rasel; Di Nicola, Corrado; Kirlikovali, Kent O.; Snurr, Randall Q.; Farha, Omar K.

doi:10.1021/acs.cgd.4c00287

Title: Constraining Flexibility in the MIL-88 Topology through Integration of 3-Dimensional Linkers

Journal Article · 16 April 2024 · Crystal Growth and Design

DOI: https://doi.org/10.1021/acs.cgd.4c00287 · OSTI ID:2467579

^[1];

^[2]; Campitelli, Patrizio ^[3];

^[2]; Eddaoudi, Manel A. ^[2]; Mian, Mohammad Rasel ^[2];

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^[2];

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Northwestern University, Evanston, IL (United States); University of Chicago
Northwestern University, Evanston, IL (United States)
University of L′Aquila (Italy)
University of Camerino (Italy)

Metal–organic frameworks (MOFs) are a class of crystalline, nanoporous materials that are recognized for their tunability. While some MOFs demonstrate flexibility, this characteristic can pose challenges in achieving precise pore control or establishing permanent porosity. Specifically, MIL-88B, is notable for its high flexibility, as it is constructed from metal trimer clusters and 2-dimensional linkers (2DLs) featuring planar, aromatic cores, allowing significant structural changes. In this study, we synthesized two new MOFs, NU-2010 and NU-2011, which are structurally analogous to MIL-88B but incorporate ditopic 3-dimensional linkers (3DLs) with sterically bulky cores and higher symmetry. Our aim was to investigate whether the introduction of 3DLs could mitigate the flexibility observed in MIL-88B. We employed a combination of single crystal and powder X-ray diffraction techniques to assess the flexibility of MIL-88B, NU-2010, and NU-2011 under various conditions including thermal activation, solvent exchange, and temperature changes. Furthermore, our findings indicate that incorporating 3DLs significantly reduces framework flexibility in NU-2010 and NU-2011 relative to MIL-88B.

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Research Organization:: University of Chicago, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-08ER15967; SC0023383

OSTI ID:: 2467579

Journal Information:: Crystal Growth and Design, Journal Name: Crystal Growth and Design Journal Issue: 9 Vol. 24; ISSN 1528-7483

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical structure
Crystal structure
Diffraction
Metal organic frameworks
Solvents

CCDC 2332772: Experimental Crystal Structure Determination S., Smoljan, Courtney; Fanrui, Sha,; Patrizio, Campitelli, https://doi.org/10.5517/ccdc.csd.cc2j9fq0 The current record is supplemented by this dataset	dataset	January 2024
CCDC 2332773: Experimental Crystal Structure Determination S., Smoljan, Courtney; Fanrui, Sha,; Patrizio, Campitelli, https://doi.org/10.5517/ccdc.csd.cc2j9fr1 The current record is supplemented by this dataset	dataset	January 2024
CCDC 2332774: Experimental Crystal Structure Determination S., Smoljan, Courtney; Fanrui, Sha,; Patrizio, Campitelli, https://doi.org/10.5517/ccdc.csd.cc2j9fs2 The current record is supplemented by this dataset	dataset	January 2024
CCDC 2332775: Experimental Crystal Structure Determination S., Smoljan, Courtney; Fanrui, Sha,; Patrizio, Campitelli, https://doi.org/10.5517/ccdc.csd.cc2j9ft3 The current record is supplemented by this dataset	dataset	January 2024
CCDC 2332776: Experimental Crystal Structure Determination S., Smoljan, Courtney; Fanrui, Sha,; Patrizio, Campitelli, https://doi.org/10.5517/ccdc.csd.cc2j9fv4 The current record is supplemented by this dataset	dataset	January 2024
CCDC 2332777: Experimental Crystal Structure Determination S., Smoljan, Courtney; Fanrui, Sha,; Patrizio, Campitelli, https://doi.org/10.5517/ccdc.csd.cc2j9fw5 The current record is supplemented by this dataset	dataset	January 2024
CCDC 2332778: Experimental Crystal Structure Determination S., Smoljan, Courtney; Fanrui, Sha,; Patrizio, Campitelli, https://doi.org/10.5517/ccdc.csd.cc2j9fx6 The current record is supplemented by this dataset	dataset	January 2024
CCDC 2332779: Experimental Crystal Structure Determination S., Smoljan, Courtney; Fanrui, Sha,; Patrizio, Campitelli, https://doi.org/10.5517/ccdc.csd.cc2j9fy7 The current record is supplemented by this dataset	dataset	January 2024
CCDC 2332780: Experimental Crystal Structure Determination S., Smoljan, Courtney; Fanrui, Sha,; Patrizio, Campitelli, https://doi.org/10.5517/ccdc.csd.cc2j9fz8 The current record is supplemented by this dataset	dataset	January 2024

Title: Constraining Flexibility in the MIL-88 Topology through Integration of 3-Dimensional Linkers

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References (28)

Linked Research (9)

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