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Nano Research 2021, 14(2): 417-422 https://doi.org/10.1007/s12274-020-3123-z
Research Article | Issue | Published: 19 October 2020

Applying reticular synthesis to the design of Cu-based MOFs with mechanically interlocked linkers

Show Author's Information Alexander J. Stirk1,  Benjamin H. Wilson1,  Christopher A. O’Keefe1,  Hazem Amarne2,  Kelong Zhu3,  Robert W. Schurko4,  Stephen J. Loeb1,( )
Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ontario, N9B 3B4, Canada
Department of Chemistry, The University of Jordan, Amman, 11942, Jordan
School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA
Keywords:
metal-organic frameworks, reticular chemistry, mechanically interlocked molecules, rotaxane
Topics:
Copper compoundsMetalsNuclear magnetic resonance spectroscopyOrganic frameworks OrganometallicsSingle crystals
Cite this article:
Stirk AJ, Wilson BH, O’Keefe CA, et al. Applying reticular synthesis to the design of Cu-based MOFs with mechanically interlocked linkers. Nano Research, 2021, 14(2): 417-422. https://doi.org/10.1007/s12274-020-3123-z
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Abstract Full text Electronic supplementary material About this article

The concept of "robust dynamics" describes the incorporation of mechanically interlocked molecules (MIMs) into metal-organic framework (MOF) materials such that large amplitude motions (e.g., rotation or translation of a macrocycle) can occur inside the free volume pore of the MOF. To aid in the preparation of such materials, reticular synthesis was used herein to design rigid molecular building blocks with predetermined ordered structures starting from the well-known MOF NOTT-101. New linkers were synthesized that have a T-shape, based on a triphenylene tetracarboxylate strut, and their incorporation into Cu(II)-based MOFs was investigated. The single-crystal structures of three new MOFs, UWCM-12 (fof), β-UWCM-13 (loz), UWCM-14 (lil), with naked T-shaped linkers were determined; β-UWCM-13 is the first reported example of the loz topology. A fourth MOF, UWDM-14 (lil) is analogous to UWCM-14 (lil) but contains a [2]rotaxane linker. Variable-temperature, 2H solid-state NMR was used to probe the dynamics of a 24-membered macrocycle threaded onto the MOF skeleton.


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Electronic supplementary material
About this article

Applying reticular synthesis to the design of Cu-based MOFs with mechanically interlocked linkers

Show Author's information Alexander J. Stirk1, Benjamin H. Wilson1, Christopher A. O’Keefe1, Hazem Amarne2, Kelong Zhu3, Robert W. Schurko4, Stephen J. Loeb1,( )
Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ontario, N9B 3B4, Canada
Department of Chemistry, The University of Jordan, Amman, 11942, Jordan
School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA

Abstract

The concept of "robust dynamics" describes the incorporation of mechanically interlocked molecules (MIMs) into metal-organic framework (MOF) materials such that large amplitude motions (e.g., rotation or translation of a macrocycle) can occur inside the free volume pore of the MOF. To aid in the preparation of such materials, reticular synthesis was used herein to design rigid molecular building blocks with predetermined ordered structures starting from the well-known MOF NOTT-101. New linkers were synthesized that have a T-shape, based on a triphenylene tetracarboxylate strut, and their incorporation into Cu(II)-based MOFs was investigated. The single-crystal structures of three new MOFs, UWCM-12 (fof), β-UWCM-13 (loz), UWCM-14 (lil), with naked T-shaped linkers were determined; β-UWCM-13 is the first reported example of the loz topology. A fourth MOF, UWDM-14 (lil) is analogous to UWCM-14 (lil) but contains a [2]rotaxane linker. Variable-temperature, 2H solid-state NMR was used to probe the dynamics of a 24-membered macrocycle threaded onto the MOF skeleton.

Keywords: metal-organic frameworks, reticular chemistry, mechanically interlocked molecules, rotaxane

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Publication history
Copyright
Acknowledgements

Publication history

Received: 19 August 2020
Revised: 12 September 2020
Accepted: 14 September 2020
Published: 19 October 2020
Issue date: February 2021

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature

Acknowledgements

S. J. L. acknowledges the Natural Sciences and Engineering Research Council of Canada for support of a Discovery Grant (101694) and a Canada Research Chair. R. W. S. is also grateful for support from NSERC, the Canadian Foundation for Innovation, the Ontario Innovation Trust, the University of Windsor for the development and maintenance of the SSNMR centre, and for funding from the Florida State University and the National High Magnetic Field Laboratory (NHMFL), which is funded by the National Science Foundation Cooperative Agreement (DMR-1644779) and by the State of Florida. The authors acknowledge M. Revington for technical assistance with solution NMR spectroscopy and J. Auld for technical assistance with high resolution mass spectrometry.

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