The Mechanochemical Reset for Coordination Self-Assembly.
Abstract
Self-assembly is a canonical process for generating ordered, functional architectures, with the structural 'blueprint' encoded in the component design and interaction thermodynamics. While external stimuli such as concentration and chemical guests might shift the equilibrium between predefined ordered states, the structural memory remains embedded in the assembly (thermodynamic control). In this work, we employ mechanical force as a unique stimulus to dismantle thermodynamic order, accessing a structural “erasing” state and resetting the assembly landscape. Specifically, ball-milling of a thermodynamically-preferred Pd6L14 coordination cage (c-Pd6L14) drives it to a disordered, ligand-exchanged state (PdxL1y), which upon dissolution undergoes a conversion to a transient and metastable tubular Pd6L14 isomer (t-Pd6L14), thermodynamically inaccessible from conventional pathways from c-Pd6L14.We generalize such “mechanochemical reset” by transforming a complex double-walled Pd12L28 knot-like cage into a triply interlocked [Pd3L22]2 complex via a similar force-generated disordered PdxL2y state. To highlight the uniqueness of the reset process, this strategy was further employed in two confinement catalytic settings: 1) thermal; and 2) photochemical C-H oxidation reactions, where the analogous reactions suffer from product inhibition in conventional conditions. This work establishes mechanochemistry as not merely a green synthetic tool, but a powerful strategy for escaping deep thermodynamic minima and navigating the self-assembly energy landscape toward non-thermodynamic, otherwise-inaccessible states.
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BibTeX
@misc{li2026mechanochemical,
title = {{The Mechanochemical Reset for Coordination Self-Assembly.}},
author = {Shi Li and Fang-Zi Liu and Xinhan Liu and Yan Liu and Peiyi Wang and KaKing Yan},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008331/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008331/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - The Mechanochemical Reset for Coordination Self-Assembly.
AU - Shi Li
AU - Fang-Zi Liu
AU - Xinhan Liu
AU - Yan Liu
AU - Peiyi Wang
AU - KaKing Yan
PY - 2026
DA - 2026/09/04
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008331/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008331/v1
AB - Self-assembly is a canonical process for generating ordered, functional architectures, with the structural 'blueprint' encoded in the component design and interaction thermodynamics. While external stimuli such as concentration and chemical guests might shift the equilibrium between predefined ordered states, the structural memory remains embedded in the assembly (thermodynamic control). In this work, we employ mechanical force as a unique stimulus to dismantle thermodynamic order, accessing a structural “erasing” state and resetting the assembly landscape. Specifically, ball-milling of a thermodynamically-preferred Pd6L14 coordination cage (c-Pd6L14) drives it to a disordered, ligand-exchanged state (PdxL1y), which upon dissolution undergoes a conversion to a transient and metastable tubular Pd6L14 isomer (t-Pd6L14), thermodynamically inaccessible from conventional pathways from c-Pd6L14.We generalize such “mechanochemical reset” by transforming a complex double-walled Pd12L28 knot-like cage into a triply interlocked [Pd3L22]2 complex via a similar force-generated disordered PdxL2y state. To highlight the uniqueness of the reset process, this strategy was further employed in two confinement catalytic settings: 1) thermal; and 2) photochemical C-H oxidation reactions, where the analogous reactions suffer from product inhibition in conventional conditions. This work establishes mechanochemistry as not merely a green synthetic tool, but a powerful strategy for escaping deep thermodynamic minima and navigating the self-assembly energy landscape toward non-thermodynamic, otherwise-inaccessible states.
ER -