The Organic Secondary Building Unit: Strong Intermolecular π Interactions Define Topology in MIT-25, a Mesoporous MOF with Proton-Replete Channels

Sarah S. Park; Christopher H. Hendon; Alistair J. Fielding; Aron Walsh; Michael O’Keeffe; Mircea Dincă

doi:10.1021/jacs.6b13176

The Organic Secondary Building Unit: Strong Intermolecular π Interactions Define Topology in MIT-25, a Mesoporous MOF with Proton-Replete Channels

Sarah S. Park, Christopher H. Hendon, Alistair J. Fielding, Aron Walsh, Michael O’Keeffe, Mircea Dincă

Department of Materials Science and Engineering

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

59 Citations (Scopus)

Abstract

The structure-directing role of the inorganic secondary building unit (SBU) is key for determining the topology of metal-organic frameworks (MOFs). Here we show that organic building units relying on strong π interactions that are energetically competitive with the formation of common inorganic SBUs can also play a role in defining the topology. We demonstrate the importance of the organic SBU in the formation of Mg₂H₆(H₃O)(TTFTB)₃ (MIT-25), a mesoporous MOF with the new ssp topology. A delocalized electronic hole is critical in the stabilization of the TTF triad organic SBUs and exemplifies a design principle for future MOF synthesis.

Original language	English
Pages (from-to)	3619-3622
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	139
Issue number	10
DOIs	https://doi.org/10.1021/jacs.6b13176
Publication status	Published - 2017 Mar 15

Bibliographical note

Funding Information:
All experimental work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (DESC0006937). M.D. gratefully acknowledges early career support from the Sloan Foundation, the Research Corporation for Science Advancement (Cottrell Scholar), and the Dreyfus Foundation. S.S.P. was partially supported by a National Science Foundation Graduate Research Fellowship (1122374). A.J.F. was supported by Bruker. All of the EPR experiments were carried out at the EPSRC National EPR Facility and Service, University of Manchester, U.K.. A.W. was supported by the ERC (277757). S.S.P. thanks M. Korzyński for providing H4TBAPy. We thank Dr. P. Müller and Dr. J. Becker for assistance with crystallography and Prof. O. Yaghi for valuable discussions. Computational work was enabled by access to XSEDE, which is supported by NSF (ACI-1053575).

Publisher Copyright:
© 2017 American Chemical Society.

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.6b13176

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title = "The Organic Secondary Building Unit: Strong Intermolecular π Interactions Define Topology in MIT-25, a Mesoporous MOF with Proton-Replete Channels",

abstract = "The structure-directing role of the inorganic secondary building unit (SBU) is key for determining the topology of metal-organic frameworks (MOFs). Here we show that organic building units relying on strong π interactions that are energetically competitive with the formation of common inorganic SBUs can also play a role in defining the topology. We demonstrate the importance of the organic SBU in the formation of Mg2H6(H3O)(TTFTB)3 (MIT-25), a mesoporous MOF with the new ssp topology. A delocalized electronic hole is critical in the stabilization of the TTF triad organic SBUs and exemplifies a design principle for future MOF synthesis.",

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note = "Funding Information: All experimental work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (DESC0006937). M.D. gratefully acknowledges early career support from the Sloan Foundation, the Research Corporation for Science Advancement (Cottrell Scholar), and the Dreyfus Foundation. S.S.P. was partially supported by a National Science Foundation Graduate Research Fellowship (1122374). A.J.F. was supported by Bruker. All of the EPR experiments were carried out at the EPSRC National EPR Facility and Service, University of Manchester, U.K.. A.W. was supported by the ERC (277757). S.S.P. thanks M. Korzy{\'n}ski for providing H4TBAPy. We thank Dr. P. M{\"u}ller and Dr. J. Becker for assistance with crystallography and Prof. O. Yaghi for valuable discussions. Computational work was enabled by access to XSEDE, which is supported by NSF (ACI-1053575). Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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The Organic Secondary Building Unit : Strong Intermolecular π Interactions Define Topology in MIT-25, a Mesoporous MOF with Proton-Replete Channels. / Park, Sarah S.; Hendon, Christopher H.; Fielding, Alistair J. et al.

In: Journal of the American Chemical Society, Vol. 139, No. 10, 15.03.2017, p. 3619-3622.

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

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The Organic Secondary Building Unit: Strong Intermolecular π Interactions Define Topology in MIT-25, a Mesoporous MOF with Proton-Replete Channels

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