Out-of-equilibrium Pd(II)-based cage populations with chiral memory
Abstract
Metallosupramolecular assembly has considerably progressed the rational creation of complex nano structures. Yet, their use has remained largely constrained to operating under thermodynamic control, far from reaching the functional sophistication seen in out-of-equilibrium biological systems. Here, we show that populations of heteroleptic Pd2L4-type coordination cages can be transiently and repeatedly driven out of equilibrium using a chiral cage-based chemical fuel and C 60 fullerene as an anti-fuel. This fueling cycle allows a temporary assembly to be formed through competition between ligand exchange and guest encapsulation reactions, operating at different timescales. The system behaves as an energy ratchet and can be refueled. At the center of the assembly, a chiral figure-of-eight motif formed by red diketopyrrolopyrrole ligands partially retains its handedness during ligand exchange, leading to a chiral memory effect. This work establishes chemically fueled coordination cage populations as a versatile basis for encoding transient structural and stereochemical information within complex dynamic systems.
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BibTeX
@misc{benchimol2026outofequilibrium,
title = {{Out-of-equilibrium Pd(II)-based cage populations with chiral memory}},
author = {Elie Benchimol and Björn Schmidt and Irene Regeni and Thorfinnur Gunnlaugsson and Guido H. Clever},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15009694/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009694/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Out-of-equilibrium Pd(II)-based cage populations with chiral memory
AU - Elie Benchimol
AU - Björn Schmidt
AU - Irene Regeni
AU - Thorfinnur Gunnlaugsson
AU - Guido H. Clever
PY - 2026
DA - 2026/09/30
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009694/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009694/v1
AB - Metallosupramolecular assembly has considerably progressed the rational creation of complex nano structures. Yet, their use has remained largely constrained to operating under thermodynamic control, far from reaching the functional sophistication seen in out-of-equilibrium biological systems. Here, we show that populations of heteroleptic Pd2L4-type coordination cages can be transiently and repeatedly driven out of equilibrium using a chiral cage-based chemical fuel and C 60 fullerene as an anti-fuel. This fueling cycle allows a temporary assembly to be formed through competition between ligand exchange and guest encapsulation reactions, operating at different timescales. The system behaves as an energy ratchet and can be refueled. At the center of the assembly, a chiral figure-of-eight motif formed by red diketopyrrolopyrrole ligands partially retains its handedness during ligand exchange, leading to a chiral memory effect. This work establishes chemically fueled coordination cage populations as a versatile basis for encoding transient structural and stereochemical information within complex dynamic systems.
ER -