@article{47cf6ad193f744f58baf9ee5180db8f5,
title = "Diastereoselective Self‐Assembly of Low‐Symmetry PdnL2n Nanocages through Coordination‐Sphere Engineering",
abstract = "Metal‐organic cages (MOCs) are popular host architectures assembled from ligands and metal ions/nodes. Assembling structurally complex, low‐symmetry MOCs with anisotropic cavities can be limited by the formation of statistical isomer libraries. We set out to investigate the use of primary coordination‐sphere engineering (CSE) to bias isomer selectivity within homo‐ and heteroleptic Pd n L2n cages. Unexpected differences in selectivities between alternative donor groups led us to recognise the significant impact of the second coordination sphere on isomer stabilities. From this, molecular‐level insight into the origins of selectivity between cis and trans diastereoisomers was gained, highlighting the importance of both host–guest and host‐solvent interactions, in addition to ligand design. This detailed understanding allows precision engineering of low‐symmetry MOC assemblies without wholesale redesign of the ligand framework, and fundamentally provides a theoretical scaffold for the development of stimuli‐responsive, shape‐shifting MOCs.",
keywords = "Self-Assembly, Low-Symmetry, Coordination-Sphere, Metallosupramolecular Chemistry, Coordination Cages",
author = "Paulina Molinska and Andrew Tarzia and Louise Male and Jelfs, {Kim E.} and Jamie Lewis",
note = "Acknowledgments Special thanks to Dr Georgia Orton for assistance with the collection of synchrotron SCXRD data, Dr C{\'e}cile Le Duff for assistance with the collection of NMR data, Dr Christopher Williams for the collection of MS data, and Prof. Steve Goldup for useful discussions. We acknowledge Diamond Light Source for time on Beamline I19 under Proposal CY28766. AT acknowledges funding received from the European Union under the NextGenerationEU program (grant CAGEX, SOE_0000033). KEJ acknowledges the Royal Society for a University Research Fellowship and Enhancement Award and the ERC through Agreement No. 758370 (ERC-StG-PE5-CoMMaD). This work used the ARCHER2 UK National Supercomputing Service (https://www.archer2.ac.uk) via our membership of the UK's Materials Chemistry HEC Consortium, which is funded by EPSRC (EP/X035859/1), and Imperial College London's Research Computing Service, DOI: 10.14469/hpc/2232. This work was supported by the Royal Society (URF\R1\221740 and RF\ERE\221016) and the University of Birmingham. JEML is a Royal Society University Research Fellow.",
year = "2023",
month = dec,
day = "18",
doi = "10.1002/ange.202315451",
language = "English",
volume = "135",
journal = "Angewandte Chemie",
issn = "0044-8249",
publisher = "Wiley-VCH Verlag",
number = "51",
}