RT Journal Article
T1 Cooperative reversible assembly in triply interlocked Al6L4 and Ga6L4 cages
A1 Izquierdo, Ignacio
A1 Martínez Castro, Laura
A1 Ujaque, Gregori
A1 Martínez Martínez, Antonio Jesús
AB 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.
PB Royal Society of Chemistry
SN 2041-6520
SN 2041-6539 (electrónico)
YR 2025
FD 2025
LK https://hdl.handle.net/10272/27400
UL https://hdl.handle.net/10272/27400
LA eng
NO Izquierdo, I., Martínez-Castro, L., Ujaque, G., & Martínez-Martínez, A. J. (2025). Cooperative reversible assembly in triply interlocked Al6L4 and Ga6L4 cages. Chemical Science, 16(43), 20406–20413. https://doi.org/10.1039/d5sc05441a
NO 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).
DS Repositorio Institucional de la Universidad de Huelva
RD 29 may 2026