Alkali cation-π interactions in aqueous systems, modulating supramolecular stereoisomerism of nanoscopic metal-organic capsules
Abstract Contrary to common chemical intuition, cation-π interactions can persist in polar, aqueous reaction solutions, rather than in dry non-coordinative solvent systems. This account highlights how alkali ion-π interactions impart distinctive structure-influencing supramolecular forces that can b...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-11-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-54426-4 |
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| author | Paul Wix Swetanshu Tandon Sebastien Vaesen Kadri Karimu Jennifer S. Mathieson Kane Esien Solveig Felton Graeme W. Watson Wolfgang Schmitt |
| author_facet | Paul Wix Swetanshu Tandon Sebastien Vaesen Kadri Karimu Jennifer S. Mathieson Kane Esien Solveig Felton Graeme W. Watson Wolfgang Schmitt |
| author_sort | Paul Wix |
| collection | DOAJ |
| description | Abstract Contrary to common chemical intuition, cation-π interactions can persist in polar, aqueous reaction solutions, rather than in dry non-coordinative solvent systems. This account highlights how alkali ion-π interactions impart distinctive structure-influencing supramolecular forces that can be exploited in the preparation of nanoscopic metal-organic capsules. The incorporation of alkali ions from polar solutions into molecular pockets promotes the assembly of otherwise inaccessible capsular entities whose structures are distinctive to those of common polyoxovanadate clusters in which {V=O} moieties usually point radially to the outside, shielding the molecular entities. The applied concept is exemplified by homologous {V20} and {V30} cages, composed of inverted, hemispherical {V5O9} units. The number and geometrical organization of these {V5O9} sub-units in these cages are associated with prevailing cation- $$\pi$$ π interactions and competing steric effects. The stereoisomers of these resulting nano-sized objects are comparable to Alfred Werner-type structural isomers of simple mononuclear complexes in-line with fundamental coordination chemistry principles. |
| format | Article |
| id | doaj-art-5edd3fad84ac477aadfb8ced0d3bd5ef |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-11-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-5edd3fad84ac477aadfb8ced0d3bd5ef2024-11-24T12:35:16ZengNature PortfolioNature Communications2041-17232024-11-0115111110.1038/s41467-024-54426-4Alkali cation-π interactions in aqueous systems, modulating supramolecular stereoisomerism of nanoscopic metal-organic capsulesPaul Wix0Swetanshu Tandon1Sebastien Vaesen2Kadri Karimu3Jennifer S. Mathieson4Kane Esien5Solveig Felton6Graeme W. Watson7Wolfgang Schmitt8School of Chemistry & SFI AMBER Research Centre, Trinity College Dublin, The University of Dublin, College GreenSchool of Chemistry & SFI AMBER Research Centre, Trinity College Dublin, The University of Dublin, College GreenSchool of Chemistry & SFI AMBER Research Centre, Trinity College Dublin, The University of Dublin, College GreenSchool of Chemistry & SFI AMBER Research Centre, Trinity College Dublin, The University of Dublin, College GreenSchool of Chemistry, University of Glasgow, Joseph Black Building, University AveCentre for Quantum Materials and Technologies, School of Mathematics and Physics, Queen’s University BelfastCentre for Quantum Materials and Technologies, School of Mathematics and Physics, Queen’s University BelfastSchool of Chemistry & SFI AMBER Research Centre, Trinity College Dublin, The University of Dublin, College GreenSchool of Chemistry & SFI AMBER Research Centre, Trinity College Dublin, The University of Dublin, College GreenAbstract Contrary to common chemical intuition, cation-π interactions can persist in polar, aqueous reaction solutions, rather than in dry non-coordinative solvent systems. This account highlights how alkali ion-π interactions impart distinctive structure-influencing supramolecular forces that can be exploited in the preparation of nanoscopic metal-organic capsules. The incorporation of alkali ions from polar solutions into molecular pockets promotes the assembly of otherwise inaccessible capsular entities whose structures are distinctive to those of common polyoxovanadate clusters in which {V=O} moieties usually point radially to the outside, shielding the molecular entities. The applied concept is exemplified by homologous {V20} and {V30} cages, composed of inverted, hemispherical {V5O9} units. The number and geometrical organization of these {V5O9} sub-units in these cages are associated with prevailing cation- $$\pi$$ π interactions and competing steric effects. The stereoisomers of these resulting nano-sized objects are comparable to Alfred Werner-type structural isomers of simple mononuclear complexes in-line with fundamental coordination chemistry principles.https://doi.org/10.1038/s41467-024-54426-4 |
| spellingShingle | Paul Wix Swetanshu Tandon Sebastien Vaesen Kadri Karimu Jennifer S. Mathieson Kane Esien Solveig Felton Graeme W. Watson Wolfgang Schmitt Alkali cation-π interactions in aqueous systems, modulating supramolecular stereoisomerism of nanoscopic metal-organic capsules Nature Communications |
| title | Alkali cation-π interactions in aqueous systems, modulating supramolecular stereoisomerism of nanoscopic metal-organic capsules |
| title_full | Alkali cation-π interactions in aqueous systems, modulating supramolecular stereoisomerism of nanoscopic metal-organic capsules |
| title_fullStr | Alkali cation-π interactions in aqueous systems, modulating supramolecular stereoisomerism of nanoscopic metal-organic capsules |
| title_full_unstemmed | Alkali cation-π interactions in aqueous systems, modulating supramolecular stereoisomerism of nanoscopic metal-organic capsules |
| title_short | Alkali cation-π interactions in aqueous systems, modulating supramolecular stereoisomerism of nanoscopic metal-organic capsules |
| title_sort | alkali cation π interactions in aqueous systems modulating supramolecular stereoisomerism of nanoscopic metal organic capsules |
| url | https://doi.org/10.1038/s41467-024-54426-4 |
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