@misc{10481/107381,
year = {2025},
month = {10},
url = {https://hdl.handle.net/10481/107381},
abstract = {Metal–organic frameworks (MOFs) based on highly connected nets continue to expand the landscape of
reticular chemistry, with zirconium (Zr) and rare-earth (RE) clusters offering ideal nodes for the
construction of robust and structurally diverse materials. While desymmetrisation of tetratopic linkers has
recently emerged as a promising approach to accessing new framework topologies, the underlying
principles governing cluster connectivity remain poorly understood. Here, we systematically investigate the
effect of linker desymmetrisation on the assembly of Zr- and RE-MOFs. A literature survey of planar
tetratopic linkers revealed that geometric parameters such as height-to-width ratio and torsion angles play
a key role in dictating cluster connectivity. Guided by these insights, we designed two new nanosized
tetratopic ligands with enhanced conformational flexibility, enabling the synthesis of six MOFs with diverse
cluster types and topologies. These include three Zr-MOFs, two featuring 8-connected (8-c) Zr6 clusters
with csq and scu topologies, and one with a rare 4-c Zr cluster, and three RE-MOFs, including one with an
unprecedented heptanuclear RE cluster forming a 4,8L15 net. Finally, we demonstrate that frameworks with
accessible metal clusters, such as the csq-Zr-MOF and 4,8L15-RE-MOF, show outstanding catalytic activity
in the hydrolysis of P–F bonds in G-type nerve agent simulants. These results highlight linker
desymmetrisation as a powerful strategy for tuning both structure and function in MOFs.},
organization = {European Union – Horizon 2020 research and innovation programme (grant agreement no. 101019003)},
organization = {MCIN/AEI/10.13039/501100011033 – ERDF “A way of making Europe” (Grant Ref. PID2021-124804NB-I00)},
organization = {ALBA Synchrotron – beamtime access (proposal ID 20250330096)},
organization = {Catalan Government – AGAUR (project 2021 SGR 00458)},
organization = {MCIN/AEI/10.13039/501100011033  (Grant CEX2021-001214-S)},
organization = {Spanish Ministry of Education – predoctoral fellowship (FPU23/01844)},
organization = {Ministerio de Ciencia, Innovación y Universidades – FPU predoctoral contracts (FPU17/00688, FPU23/91844)},
organization = {MCIN/AEI/10.13039/501100011033 – European Union NextGenerationEU/PRTR – RyC contract (RYC-2016-20187)},
organization = {European Union – Horizon Europe research and innovation programme – Marie Skłodowska-Curie Actions Postdoctoral Fellowship (Grant Agreement No. 101208213, MUVCATMOF, HORIZON-MSCA-2024-PF-01-01)},
publisher = {Royal Society of Chemistry},
title = {Linker desymmetrisation unlocks new topologies, defective clusters, and catalytic activity in zirconium- and rare-earth metal–organic frameworks},
doi = {10.1039/d5sc05365j},
author = {Ortín Rubio, Borja and Yang, Yunhui and Borrego Marin, Emilio and Rostoll Berenguer, Jaume and Vila, Carlos and Juanhuix, Judith and Imaz, Inhar and Rodríguez Navarro, Jorge Andrés and Maspoch, Daniel},
}