Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2023 Aug 9;145(31):17398-17405.
doi: 10.1021/jacs.3c05469. Epub 2023 Jul 26.

Isoreticular Contraction of Metal-Organic Frameworks Induced by Cleavage of Covalent Bonds

Yunhui Yang  1   2 , Pilar Fernández-Seriñán  1   2 , Inhar Imaz  1   2 , Felipe Gándara  3 , Marcel Handke  1   2 , Borja Ortín-Rubio  1   2 , Judith Juanhuix  4 , Daniel Maspoch  1   2   5
Affiliations

Isoreticular Contraction of Metal-Organic Frameworks Induced by Cleavage of Covalent Bonds

Yunhui Yang et al. J Am Chem Soc. .

Abstract

Isoreticular chemistry, in which the organic or inorganic moieties of reticular materials can be replaced without destroying their underlying nets, is a key concept for synthesizing new porous molecular materials and for tuning or functionalization of their pores. Here, we report that the rational cleavage of covalent bonds in a metal-organic framework (MOF) can trigger their isoreticular contraction, without the need for any additional organic linkers. We began by synthesizing two novel MOFs based on the MIL-142 family, (In)BCN-20B and (Sc)BCN-20C, which include cleavable as well as noncleavable organic linkers. Next, we selectively and quantitatively broke their cleavable linkers, demonstrating that various dynamic chemical and structural processes occur within these structures to drive the formation of isoreticular contracted MOFs. Thus, the contraction involves breaking of a covalent bond, subsequent breaking of a coordination bond, and finally, formation of a new coordination bond supported by structural behavior. Remarkably, given that the single-crystal character of the parent MOF is retained throughout the entire transformation, we were able to monitor the contraction by single-crystal X-ray diffraction.

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Schematic of the isoreticular contraction of (In)BCN-20B and (Sc)BCN-20C induced by cleavage of covalent bonds.
Figure 2
Figure 2
(a) Crystal structure of (In)BCN-20B. (b) Schematic of the stepwise isoreticular contraction from (In)BCN-20B (left) to (In)BCN-20B′ (middle) to (In)BCN-20A (right). Corresponding SCXRD data, revealing the octahedral cages viewed along the crystallographic c and b axes, highlighting transformation of the CCA linker (orange) to the shorter BDC linker (violet), and contraction of the triangular face. (c) Crystal structure of (In)BCN-20A.
Figure 3
Figure 3
(a) PXRD patterns of simulated (black) and experimental (orange) (In)BCN-20B; simulated (gray) and experimental (cyan) (In)BCN-20B′; and simulated (light gray) and experimental (violet) (In)BCN-20A. (b) 1H-NMR spectra of (In)BCN-20B (orange), (In)BCN-20B′ (cyan), and (In)BCN-20A (violet). The protons from olefinic bonds and terephthalate have been highlighted in orange and violet, respectively. (c) Infrared spectra of (In)BCN-20B (orange), (In)BCN-20B′ (cyan), and (In)BCN-20A (violet).
Figure 4
Figure 4
(a) Crystal structure of (Sc)BCN-20C. (b) Schematic and corresponding SCXRD structures of the stepwise isoreticular contraction from (Sc)BCN-20C (top) to (Sc)BCN-20C′ (middle) to (Sc)BCN-20A (down). (c) Crystal structure of (Sc)BCN-20A.
See this image and copyright information in PMC

References

    1. Zhou H.-C.; Long J. R.; Yaghi O. M. Introduction to Metal–Organic Frameworks. Chem. Rev. 2012, 112, 673–674. 10.1021/cr300014x. - DOI - PubMed
    1. Howarth A. J.; Liu Y.; Li P.; Li Z.; Wang T. C.; Hupp J. T.; Farha O. K. Chemical, thermal and mechanical stabilities of metal–organic frameworks. Nat. Rev. Mater. 2016, 1, 15018.10.1038/natrevmats.2015.18. - DOI
    1. Yaghi O. M.; O’Keeffe M.; Ockwig N. W.; Chae H. K.; Eddaoudi M.; Kim J. Reticular synthesis and the design of new materials. Nature 2003, 423, 705–714. 10.1038/nature01650. - DOI - PubMed
    1. Chen Z.; Hanna S. L.; Redfern L. R.; Alezi D.; Islamoglu T.; Farha O. K. Reticular chemistry in the rational synthesis of functional zirconium cluster-based MOFs. Coord. Chem. Rev. 2019, 386, 32–49. 10.1016/j.ccr.2019.01.017. - DOI
    1. Jiang H.; Alezi D.; Eddaoudi M. A reticular chemistry guide for the design of periodic solids. Nat. Rev. Mater. 2021, 6, 466–487. 10.1038/s41578-021-00287-y. - DOI