Lithium chloride selective ion-pair recognition by heteroditopic [2]rotaxanes †
The first heteroditopic [2]rotaxane host systems capable of strong and selective binding of lithium chloride ion-pair species are described. Importantly, a cooperative ‘switch on’ mechanism was found to operate, in which complexation of a lithium metal cation enhances the halide anion affinity of th...
| Main Authors: | , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
Royal Society of Chemistry
2024
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| _version_ | 1811140439253712896 |
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| author | Munasinghe, VK Tay, HM Manawadu, D Pancholi, J Zhang, Z Beer, PD |
| author_facet | Munasinghe, VK Tay, HM Manawadu, D Pancholi, J Zhang, Z Beer, PD |
| author_sort | Munasinghe, VK |
| collection | OXFORD |
| description | The first heteroditopic [2]rotaxane host systems capable of strong and selective binding of lithium chloride ion-pair species are described. Importantly, a cooperative ‘switch on’ mechanism was found to operate, in which complexation of a lithium metal cation enhances the halide anion affinity of the rotaxanes via a combination of favourable proximal electrostatic and preorganised allosteric effects. The mechanically bonded rotaxane host design features a macrocycle component possessing a 2,6-dialkoxy pyridyl cation binding motif and an isophthalamide anion binding group, as well as an axle component functionalised with either a halogen bonding (XB) iodotriazole or hydrogen bonding (HB) prototriazole moiety. Extensive quantitative 1H NMR titration studies in CD3CN/CDCl3 solvent mixtures determined enhanced ion-pair binding affinities for lithium halides over the corresponding sodium or potassium halide salts, with the axle prototriazole-containing HB rotaxane in particular demonstrating a marked selectivity for lithium chloride. Solid-state X-ray crystallographic studies and computational DFT investigations provide evidence for a [2]rotaxane host axle-separated ion-pair binding mode, in which complementary cation and anion binding motifs from both the macrocycle and axle components act convergently to recognise each of the charged guest species. |
| first_indexed | 2024-09-25T04:22:00Z |
| format | Journal article |
| id | oxford-uuid:5d05d5df-5b6d-49a5-8ee1-cd72b17ecc48 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-09-25T04:22:00Z |
| publishDate | 2024 |
| publisher | Royal Society of Chemistry |
| record_format | dspace |
| spelling | oxford-uuid:5d05d5df-5b6d-49a5-8ee1-cd72b17ecc482024-08-08T19:39:58ZLithium chloride selective ion-pair recognition by heteroditopic [2]rotaxanes †Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:5d05d5df-5b6d-49a5-8ee1-cd72b17ecc48EnglishJisc Publications RouterRoyal Society of Chemistry2024Munasinghe, VKTay, HMManawadu, DPancholi, JZhang, ZBeer, PDThe first heteroditopic [2]rotaxane host systems capable of strong and selective binding of lithium chloride ion-pair species are described. Importantly, a cooperative ‘switch on’ mechanism was found to operate, in which complexation of a lithium metal cation enhances the halide anion affinity of the rotaxanes via a combination of favourable proximal electrostatic and preorganised allosteric effects. The mechanically bonded rotaxane host design features a macrocycle component possessing a 2,6-dialkoxy pyridyl cation binding motif and an isophthalamide anion binding group, as well as an axle component functionalised with either a halogen bonding (XB) iodotriazole or hydrogen bonding (HB) prototriazole moiety. Extensive quantitative 1H NMR titration studies in CD3CN/CDCl3 solvent mixtures determined enhanced ion-pair binding affinities for lithium halides over the corresponding sodium or potassium halide salts, with the axle prototriazole-containing HB rotaxane in particular demonstrating a marked selectivity for lithium chloride. Solid-state X-ray crystallographic studies and computational DFT investigations provide evidence for a [2]rotaxane host axle-separated ion-pair binding mode, in which complementary cation and anion binding motifs from both the macrocycle and axle components act convergently to recognise each of the charged guest species. |
| spellingShingle | Munasinghe, VK Tay, HM Manawadu, D Pancholi, J Zhang, Z Beer, PD Lithium chloride selective ion-pair recognition by heteroditopic [2]rotaxanes † |
| title | Lithium chloride selective ion-pair recognition by heteroditopic [2]rotaxanes † |
| title_full | Lithium chloride selective ion-pair recognition by heteroditopic [2]rotaxanes † |
| title_fullStr | Lithium chloride selective ion-pair recognition by heteroditopic [2]rotaxanes † |
| title_full_unstemmed | Lithium chloride selective ion-pair recognition by heteroditopic [2]rotaxanes † |
| title_short | Lithium chloride selective ion-pair recognition by heteroditopic [2]rotaxanes † |
| title_sort | lithium chloride selective ion pair recognition by heteroditopic 2 rotaxanes † |
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