Farmer, Grace SG, Cheney, Daniel J, Truong, Khai-Nghi, Gedikoglu, Nusik, Mali, Bhupendra P 
ORCID: 0000-0002-1699-4877, Markad, Datta, Antypov, Dmytro ORCID: 0000-0003-1893-7785, Blanc, Frederic ORCID: 0000-0001-9171-1454, Katsoulidis, Alexandros P ORCID: 0000-0003-0860-7440 and Rosseinsky, Matthew J ORCID: 0000-0002-1910-2483
(2025)
Ordering Bent and Straight Dicarboxylate Linkers in an fcu Zirconium Metal-Organic Framework
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 147 (31).
pp. 27586-27598.
ISSN 0002-7863, 1520-5126
Abstract
The ordering of multiple organic linkers with different sizes and geometries on metal–organic frameworks (MOFs) offers structures with advanced complexity and functionality for enhanced properties. The selection of the components and the number of synthesis steps are commonly rationalized to match existing structural motifs in order to increase the probability of producing the designed new frameworks. Alternatively, combining multiple components, without a preconceived structural model, allows for the exploration of unprecedented structural characteristics. However, this approach requires a large number of experiments to identify both the composition and conditions for a successful synthesis. Here, we report a new Zr-MOF containing ordered straight and bent dicarboxylate linkers prepared by a one-pot synthesis. The discovery was made by high-throughput exploration of the chemical space composed of two linkers, the source of Zr, and the modulator. The linkers and the Zr<inf>6</inf> cluster are ordered on an fcu framework that is tetragonally distorted from its typical cubic symmetry. The arrangement of linkers with different sizes and geometries affords cages and windows with shapes that have not been reported previously, despite the plethora of known fcu-based MOFs. The new MOF exhibits chromatographic separation of the n-hexane/benzene/cyclohexane mixture and demonstrates reversible unbinding and rebinding of the bent linkers upon the addition and removal of protic solvents. The unusual structural properties of the new MOF arise from ordering linkers in a non-predetermined manner following high-throughput synthesis exploration.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | 3402 Inorganic Chemistry, 34 Chemical Sciences |
| Divisions: | Faculty of Science & Engineering Faculty of Science & Engineering > School of Physical Sciences |
| Depositing User: | Symplectic Admin |
| Date Deposited: | 31 Jul 2025 09:42 |
| Last Modified: | 23 May 2026 10:26 |
| DOI: | 10.1021/jacs.5c05854 |
| Open Access URL: | https://pubs.acs.org/doi/10.1021/jacs.5c05854 |
| Related Websites: | |
| URI: | https://livrepository.liverpool.ac.uk/id/eprint/3193842 |
| Disclaimer: | The University of Liverpool is not responsible for content contained on other websites from links within repository metadata. Please contact us if you notice anything that appears incorrect or inappropriate. |
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