Discovery of spontaneous de-interpenetration through charged point-point repulsions

Sylvia L. Hanna; Saumil Chheda; Ryther Anderson; Debmalya Ray; Christos D. Malliakas; Julia G. Knapp; Ken ichi Otake; Peng Li; Penghao Li; Xingjie Wang; Megan C. Wasson; Katarina Zosel; Austin M. Evans; Lee Robison; Timur Islamoglu; Xuan Zhang; William R. Dichtel; J. Fraser Stoddart; Diego A. Gomez-Gualdron; Laura Gagliardi; Omar K. Farha

doi:10.1016/j.chempr.2021.10.027

Discovery of spontaneous de-interpenetration through charged point-point repulsions

Sylvia L. Hanna, Saumil Chheda, Ryther Anderson, Debmalya Ray, Christos D. Malliakas, Julia G. Knapp, Ken ichi Otake, Peng Li, Penghao Li, Xingjie Wang, Megan C. Wasson, Katarina Zosel, Austin M. Evans, Lee Robison, Timur Islamoglu, Xuan Zhang, William R. Dichtel, J. Fraser Stoddart, Diego A. Gomez-Gualdron, Laura GagliardiOmar K. Farha^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

13 Scopus citations

Abstract

Energetically driven reduction of porosity through entanglement is ubiquitous in nature and synthetic systems. This entanglement decreases valuable internal pore space useful for applications, such as catalysis, storage, and sensing. Here, we describe the discovery of spontaneous de-interpenetration in a 6-fold interpenetrated uranium-based metal-organic framework (MOF), NU-1303-6. De-interpenetration transforms NU-1303-6 (14.2 and 19.8 Å pores) to its larger pore (40.7 Å) non-interpenetrated counterpart, which possesses a record-high 96.6% void fraction and 9.2 cm³g⁻¹ pore volume. Density functional theory calculations reveal that charged point-point repulsions between anionic, closely positioned uranium-based nodes drive this phenomenon. These repulsions compete with water molecules that hydrogen bond nearby networks together, favoring interpenetration. Controlling the interplay between these intermolecular forces enables the reversal of omnipresent energetic equilibria, leading to thermodynamically favored open pore structures. The discovery of charged point-point repulsion will likely lead to the re-evaluation of non-interpenetrated network design, synthesis, and wide-reaching applications.

Original language	English (US)
Pages (from-to)	225-242
Number of pages	18
Journal	Chem
Volume	8
Issue number	1
DOIs	https://doi.org/10.1016/j.chempr.2021.10.027
State	Published - Jan 13 2022

Funding

O.K.F. S.L.H. S.C. D.R. Peng Li, J.G.K. and L.G. acknowledge support from the U.S. Department of Energy, National Nuclear Security Administration, under award number DE-NA0003763. D.A.G.-G. acknowledges funding from NSF CAREER under award number CBET 1846707. K.O. T.I. and X.Z. acknowledge support from the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Science, Basic Energy Sciences under award number DE-SC0012702. L.R. acknowledges support from the Air Force Research Laboratory (FA8650-15-2-5518). Penghao Li. and J.F.S. thank the Northwestern University (NU) for financial support. This work made use of the International Institute for Nanotechnology (IIN); IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), the State of Illinois, Northwestern University, and the IIN; Northwestern University Quantitative Bio-Element Imaging Center generously supported by NASA Ames Research Center grant NNA04CC36G; the Mio supercomputer cluster maintained by the Colorado School of Mines where non-periodic DFT simulations (i.e. linker optimizations) were performed. S.L.H. acknowledges support from the International Institute for Nanotechnology (IIN) Ryan Fellowship and the U.S. Department of Energy National Nuclear Security Administration Stewardship Science Graduate Fellowship (DOE NNSA SSGF) under award number DE-NA0003960. J.G.K. (DGE-1842165), M.C.W. (DGE-1842165), and A.M.E. (DGE-1324585) are supported by the National Science Foundation Graduate Research Fellowship. S.L.H. thanks Louis R. Redfern, Chung-Wei Kung, and Riki J. Drout for scientific discussions during the entire project; Matthew G. Cowan, Nathaniel V. Nucci, Timothy D. Vaden, and Margaret E. Schott for manuscript review in the late stages of the project; Charlotte Stern for discussions regarding structure refinements; Kent Kirlikovali and Rodrigo Maldonado for advice regarding linker synthesis; Zhijie Chen for data visualization advice. We thank Joshua Zhu for assistance with anhydrous solvent, Marek Majewski for assistance with linker synthesis at the very early stage of the project, and Haoyuan Chen for performing a MOF database search. O.K.F. supervised the project; S.L.H. and O.K.F. conceived the project and led the investigation. S.L.H. O.K.F. X.Z. and T.I. designed the experiments and interpreted the results, with help from J.G.K.; S.L.H. synthesized ligand and MOFs, performed MOF characterization, and conducted all activation, gas adsorption, and PXRD experiments, with help from J.G.K.; S.C. and D.R. designed the computational models and performed free energy of de-interpenetration DFT calculations, as well as the EDA under the supervision of L.G.; R.A. performed pore-size distribution (PSD) calculations, void fraction calculations, and geometric surface area calculations, under the supervision of D.A.G.-G.; R.A. also performed ToBaCCo modeling, PXRD pattern matching, non-periodic DFT simulations (i.e. linker optimizations), and subsequent CIF generation with the help of K.Z. under the supervision of D.A.G.-G.; X.Z. C.D.M. J.G.K. and K.O. collected and analyzed SCXRD data, and C.D.M. performed Le Bail powder fitting; Peng Li performed Materials Studio modeling and assisted S.L.H. in MOF synthesis; Penghao Li synthesized ligand under the supervision of J.F.S.; X.W. and M.C.W. assisted S.L.H. with revision experiments. S.L.H. A.M.E. (under the supervision of W.R.D.), L.R. and O.K.F. wrote the manuscript, and all authors commented on and revised the manuscript. O.K.F. has a financial interest in NuMat Technologies, a startup company that is seeking to commercialize MOFs. All other authors declare no competing interests. One or more of the authors of this paper self-identifies as an underrepresented ethnic minority in science. One or more of the authors of this paper self-identifies as a member of the LGBTQ+ community. One or more of the authors of this paper received support from a program designed to increase minority representation in science. O.K.F., S.L.H., S.C., D.R., Peng Li, J.G.K., and L.G. acknowledge support from the U.S. Department of Energy , National Nuclear Security Administration , under award number DE-NA0003763 . D.A.G.-G. acknowledges funding from NSF CAREER under award number CBET 1846707 . K.O., T.I., and X.Z. acknowledge support from the Inorganometallic Catalyst Design Center , an EFRC funded by the DOE , Office of Science, Basic Energy Sciences under award number DE-SC0012702 . L.R. acknowledges support from the Air Force Research Laboratory ( FA8650-15-2-5518 ). Penghao Li. and J.F.S. thank the Northwestern University (NU) for financial support. This work made use of the International Institute for Nanotechnology (IIN); IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental ( SHyNE ) Resource ( NSF ECCS-2025633 ), the State of Illinois, Northwestern University , and the IIN ; Northwestern University Quantitative Bio-Element Imaging Center generously supported by NASA Ames Research Center grant NNA04CC36G ; the Mio supercomputer cluster maintained by the Colorado School of Mines where non-periodic DFT simulations (i.e., linker optimizations) were performed. S.L.H. acknowledges support from the International Institute for Nanotechnology (IIN) Ryan Fellowship and the U.S. Department of Energy National Nuclear Security Administration Stewardship Science Graduate Fellowship ( DOE NNSA SSGF ) under award number DE-NA0003960 . J.G.K. ( DGE-1842165 ), M.C.W. ( DGE-1842165 ), and A.M.E. ( DGE-1324585 ) are supported by the National Science Foundation Graduate Research Fellowship. S.L.H. thanks Louis R. Redfern, Chung-Wei Kung, and Riki J. Drout for scientific discussions during the entire project; Matthew G. Cowan, Nathaniel V. Nucci, Timothy D. Vaden, and Margaret E. Schott for manuscript review in the late stages of the project; Charlotte Stern for discussions regarding structure refinements; Kent Kirlikovali and Rodrigo Maldonado for advice regarding linker synthesis; Zhijie Chen for data visualization advice. We thank Joshua Zhu for assistance with anhydrous solvent, Marek Majewski for assistance with linker synthesis at the very early stage of the project, and Haoyuan Chen for performing a MOF database search.

Keywords

SDG7: Affordable and clean energy
charged point-point repulsion
entanglement
interpenetration
metal–organic framework
spontaneous
uranium

ASJC Scopus subject areas

General Chemistry
Biochemistry
Environmental Chemistry
General Chemical Engineering
Biochemistry, medical
Materials Chemistry

Access to Document

10.1016/j.chempr.2021.10.027

Cite this

Hanna, S. L., Chheda, S., Anderson, R., Ray, D., Malliakas, C. D., Knapp, J. G., Otake, K. I., Li, P., Li, P., Wang, X., Wasson, M. C., Zosel, K., Evans, A. M., Robison, L., Islamoglu, T., Zhang, X., Dichtel, W. R., Stoddart, J. F., Gomez-Gualdron, D. A., ... Farha, O. K. (2022). Discovery of spontaneous de-interpenetration through charged point-point repulsions. Chem, 8(1), 225-242. https://doi.org/10.1016/j.chempr.2021.10.027

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title = "Discovery of spontaneous de-interpenetration through charged point-point repulsions",

abstract = "Energetically driven reduction of porosity through entanglement is ubiquitous in nature and synthetic systems. This entanglement decreases valuable internal pore space useful for applications, such as catalysis, storage, and sensing. Here, we describe the discovery of spontaneous de-interpenetration in a 6-fold interpenetrated uranium-based metal-organic framework (MOF), NU-1303-6. De-interpenetration transforms NU-1303-6 (14.2 and 19.8 {\AA} pores) to its larger pore (40.7 {\AA}) non-interpenetrated counterpart, which possesses a record-high 96.6% void fraction and 9.2 cm3g−1 pore volume. Density functional theory calculations reveal that charged point-point repulsions between anionic, closely positioned uranium-based nodes drive this phenomenon. These repulsions compete with water molecules that hydrogen bond nearby networks together, favoring interpenetration. Controlling the interplay between these intermolecular forces enables the reversal of omnipresent energetic equilibria, leading to thermodynamically favored open pore structures. The discovery of charged point-point repulsion will likely lead to the re-evaluation of non-interpenetrated network design, synthesis, and wide-reaching applications.",

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note = "Publisher Copyright: {\textcopyright} 2021 Elsevier Inc.",

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month = jan,

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doi = "10.1016/j.chempr.2021.10.027",

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Hanna, SL, Chheda, S, Anderson, R, Ray, D, Malliakas, CD, Knapp, JG, Otake, KI, Li, P, Li, P, Wang, X, Wasson, MC, Zosel, K, Evans, AM, Robison, L, Islamoglu, T, Zhang, X, Dichtel, WR , Stoddart, JF, Gomez-Gualdron, DA, Gagliardi, L & Farha, OK 2022, 'Discovery of spontaneous de-interpenetration through charged point-point repulsions', Chem, vol. 8, no. 1, pp. 225-242. https://doi.org/10.1016/j.chempr.2021.10.027

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AU - Malliakas, Christos D.

AU - Knapp, Julia G.

AU - Otake, Ken ichi

AU - Li, Peng

AU - Li, Penghao

AU - Wang, Xingjie

AU - Wasson, Megan C.

AU - Zosel, Katarina

AU - Evans, Austin M.

AU - Robison, Lee

AU - Islamoglu, Timur

AU - Zhang, Xuan

AU - Dichtel, William R.

AU - Stoddart, J. Fraser

AU - Gomez-Gualdron, Diego A.

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AB - Energetically driven reduction of porosity through entanglement is ubiquitous in nature and synthetic systems. This entanglement decreases valuable internal pore space useful for applications, such as catalysis, storage, and sensing. Here, we describe the discovery of spontaneous de-interpenetration in a 6-fold interpenetrated uranium-based metal-organic framework (MOF), NU-1303-6. De-interpenetration transforms NU-1303-6 (14.2 and 19.8 Å pores) to its larger pore (40.7 Å) non-interpenetrated counterpart, which possesses a record-high 96.6% void fraction and 9.2 cm3g−1 pore volume. Density functional theory calculations reveal that charged point-point repulsions between anionic, closely positioned uranium-based nodes drive this phenomenon. These repulsions compete with water molecules that hydrogen bond nearby networks together, favoring interpenetration. Controlling the interplay between these intermolecular forces enables the reversal of omnipresent energetic equilibria, leading to thermodynamically favored open pore structures. The discovery of charged point-point repulsion will likely lead to the re-evaluation of non-interpenetrated network design, synthesis, and wide-reaching applications.

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Discovery of spontaneous de-interpenetration through charged point-point repulsions

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CCDC 2050154: Experimental Crystal Structure Determination

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Discovery of spontaneous de-interpenetration through charged point-point repulsions

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CCDC 2050154: Experimental Crystal Structure Determination

CCDC 2050153: Experimental Crystal Structure Determination

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