Diastereoselective Self‐Assembly of Low‐Symmetry PdnL2n Nanocages through Coordination‐Sphere Engineering

Paulina Molinska; Andrew Tarzia; Louise Male; Kim E. Jelfs; Jamie Lewis

doi:10.1002/ange.202315451

Diastereoselective Self‐Assembly of Low‐Symmetry Pd_nL_2nNanocages through Coordination‐Sphere Engineering

Paulina Molinska, Andrew Tarzia, Louise Male, Kim E. Jelfs, Jamie Lewis^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

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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.

Original language	English
Article number	e202315451
Number of pages	10
Journal	Angewandte Chemie
Early online date	27 Oct 2023
DOIs	https://doi.org/10.1002/ange.202315451
Publication status	E-pub ahead of print - 27 Oct 2023

Bibliographical note

Acknowledgments
Special thanks to Dr Georgia Orton for assistance with the collection of synchrotron SCXRD data, Dr Cécile 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.

Keywords

Self-Assembly
Low-Symmetry
Coordination-Sphere
Metallosupramolecular Chemistry
Coordination Cages

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10.1002/ange.202315451Licence: Creative Commons: Attribution (CC BY)

MolinskaP2023Diastereoselective.pdfFinal published version, 3.76 MBLicence: Creative Commons: Attribution (CC BY)

Tailorable Porous Hydrogels
Lewis, J.
The Royal Society
1/10/22 → 30/09/27
Project: Research Councils

Cite this

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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.",

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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.",

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AU - Lewis, Jamie

N1 - Acknowledgments Special thanks to Dr Georgia Orton for assistance with the collection of synchrotron SCXRD data, Dr Cécile 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.

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N2 - 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.

AB - 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.

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KW - Metallosupramolecular Chemistry

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ER -

Diastereoselective Self‐Assembly of Low‐Symmetry PdnL2n Nanocages through Coordination‐Sphere Engineering

Abstract

Bibliographical note

Keywords

Access to Document

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Projects

Tailorable Porous Hydrogels

Cite this

Diastereoselective Self‐Assembly of Low‐Symmetry Pd_nL_2nNanocages through Coordination‐Sphere Engineering