Ring-Over-Ring Deslipping From Imine-Bridged Heterorotaxanes
Ring-over-ring slippage and ring-through-ring penetration are important processes in the construction of ring-in-ring multiple interlocked architectures. We have successfully observed “ring-over-ring deslipping” on the rotaxane axle by exploiting the dynamic covalent nature of imine bonds in imine-b...
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| Format: | Article |
| Language: | English |
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Frontiers Media S.A.
2022-05-01
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| Series: | Frontiers in Chemistry |
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| Online Access: | https://www.frontiersin.org/articles/10.3389/fchem.2022.885939/full |
| _version_ | 1811234029683343360 |
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| author | Sayaka Hoshino Kosuke Ono Hidetoshi Kawai |
| author_facet | Sayaka Hoshino Kosuke Ono Hidetoshi Kawai |
| author_sort | Sayaka Hoshino |
| collection | DOAJ |
| description | Ring-over-ring slippage and ring-through-ring penetration are important processes in the construction of ring-in-ring multiple interlocked architectures. We have successfully observed “ring-over-ring deslipping” on the rotaxane axle by exploiting the dynamic covalent nature of imine bonds in imine-bridged heterorotaxanes R1 and R2 with two macrocycles of different ring sizes on the axle. When the imine bridges of R1 were cleaved, a hydrolyzed hetero[4]rotaxane [4]R1′ was formed as an intermediate under dynamic equilibrium, and the larger 38-membered macrocycle M was deslipped over the 24-membered ring (24C8 or DB24C8) to dissociate into a [3]rotaxane [3]R3 and a macrocycle M. The time dependent NMR measurement and the determined thermodynamic parameters revealed that the rate-limiting step of the deslipping process was attributed to steric hindrance between two rings and reduced mobility of M due to proximity to the crown ether, which was bound to the anilinium on the axle molecule. |
| first_indexed | 2024-04-12T11:29:39Z |
| format | Article |
| id | doaj.art-37be6854ab524949bcc15e138d9841bb |
| institution | Directory Open Access Journal |
| issn | 2296-2646 |
| language | English |
| last_indexed | 2024-04-12T11:29:39Z |
| publishDate | 2022-05-01 |
| publisher | Frontiers Media S.A. |
| record_format | Article |
| series | Frontiers in Chemistry |
| spelling | doaj.art-37be6854ab524949bcc15e138d9841bb2022-12-22T03:35:03ZengFrontiers Media S.A.Frontiers in Chemistry2296-26462022-05-011010.3389/fchem.2022.885939885939Ring-Over-Ring Deslipping From Imine-Bridged HeterorotaxanesSayaka Hoshino0Kosuke Ono1Hidetoshi Kawai2Department of Chemistry, Faculty of Science, Tokyo University of Science, Tokyo, JapanDepartment of Chemistry, Tokyo Institute of Technology, Tokyo, JapanDepartment of Chemistry, Faculty of Science, Tokyo University of Science, Tokyo, JapanRing-over-ring slippage and ring-through-ring penetration are important processes in the construction of ring-in-ring multiple interlocked architectures. We have successfully observed “ring-over-ring deslipping” on the rotaxane axle by exploiting the dynamic covalent nature of imine bonds in imine-bridged heterorotaxanes R1 and R2 with two macrocycles of different ring sizes on the axle. When the imine bridges of R1 were cleaved, a hydrolyzed hetero[4]rotaxane [4]R1′ was formed as an intermediate under dynamic equilibrium, and the larger 38-membered macrocycle M was deslipped over the 24-membered ring (24C8 or DB24C8) to dissociate into a [3]rotaxane [3]R3 and a macrocycle M. The time dependent NMR measurement and the determined thermodynamic parameters revealed that the rate-limiting step of the deslipping process was attributed to steric hindrance between two rings and reduced mobility of M due to proximity to the crown ether, which was bound to the anilinium on the axle molecule.https://www.frontiersin.org/articles/10.3389/fchem.2022.885939/fulldynamic covalent bondiminemacrocyclemolecular shuttlerotaxanesupramolecular chemistry |
| spellingShingle | Sayaka Hoshino Kosuke Ono Hidetoshi Kawai Ring-Over-Ring Deslipping From Imine-Bridged Heterorotaxanes Frontiers in Chemistry dynamic covalent bond imine macrocycle molecular shuttle rotaxane supramolecular chemistry |
| title | Ring-Over-Ring Deslipping From Imine-Bridged Heterorotaxanes |
| title_full | Ring-Over-Ring Deslipping From Imine-Bridged Heterorotaxanes |
| title_fullStr | Ring-Over-Ring Deslipping From Imine-Bridged Heterorotaxanes |
| title_full_unstemmed | Ring-Over-Ring Deslipping From Imine-Bridged Heterorotaxanes |
| title_short | Ring-Over-Ring Deslipping From Imine-Bridged Heterorotaxanes |
| title_sort | ring over ring deslipping from imine bridged heterorotaxanes |
| topic | dynamic covalent bond imine macrocycle molecular shuttle rotaxane supramolecular chemistry |
| url | https://www.frontiersin.org/articles/10.3389/fchem.2022.885939/full |
| work_keys_str_mv | AT sayakahoshino ringoverringdeslippingfromiminebridgedheterorotaxanes AT kosukeono ringoverringdeslippingfromiminebridgedheterorotaxanes AT hidetoshikawai ringoverringdeslippingfromiminebridgedheterorotaxanes |