@article{10272/27400,
year = {2025},
url = {https://hdl.handle.net/10272/27400},
abstract = {Understanding and controlling the assembly of mechanically interlocked molecules remains a significant challenge. Formation of mechanically interlocked metal–organic cages has, to date, relied exclusively on transition metals due to their predictable coordination geometries and robust bonding. Here, we report, for the first time, the reversible assembly of mechanically interlocked cages based on main-group metals, Al6L4 and Ga6L4. Structural and computational analyses reveal helical [2]catenane quadruple-decker cage topologies stabilized by six metal–ligand nodes, bridging μ-OH groups, extensive π-stacking, and directional CH⋯O interactions. Remarkably, simple acid–base cycling triggers fully reversible cage unlocking–recatenation processes in water at room temperature. Unlike transition-metal-mediated cage interlocking, they assemble instantaneously and selectively via an unprecedented cooperative main-group interlocking pathway, without detectable monomeric cage intermediates. Thermodynamic analyses reveal metal-dependent switching, involving entropy-driven disassembly coupled to strongly enthalpy-driven reassembly, with the Ga6L4 cage ∼500-fold more stable than Al6L4. These findings provide fundamental understanding of new assembly dynamics beyond conventional transition metals.},
organization = {We thank the Spanish Ministerio de Ciencia, Innovación y Universidades MICIN/AEI/10.13039/501100011033 (grant PID2023-150881NB-I00 for G. U. and PID2022-142270OBI00 for A. J. M. M.), MICIN/NextGenerationEU/PRTR (CNS2022- 136087), the European Research and Development Fund (ERDF) and the University of Huelva (EPIT1442023). I. I. acknowledges the AEI Research State Agency for an FPI Research Contract (PRE2020-094250). L. M.-C. acknowledges the support of the Generalitat de Catalunya (2021 FISDU 00034). Funding for open access was provided by the University of Huelva (CBUA).},
publisher = {Royal Society of Chemistry},
title = {Cooperative reversible assembly in triply interlocked Al6L4 and Ga6L4 cages},
doi = {10.1039/d5sc05441a},
author = {Izquierdo, Ignacio and Martínez Castro, Laura and Ujaque, Gregori and Martínez Martínez, Antonio Jesús},
}