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Lockyer, SJ, Fielding, AJ, Whitehead, GFS, Timco, GA, Winpenny, REP and McInnes, EJL (2019) Close Encounters of the Weak Kind: Investigations of Electron-Electron Interactions between Dissimilar Spins in Hybrid Rotaxanes. Journal of the American Chemical Society, 141 (37). pp. 14633-14642. ISSN 0002-7863
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Abstract
We report a family of hybrid [2]rotaxanes based on inorganic [Cr7NiF8(O2C t Bu)16]- ("{Cr7Ni}") rings templated about organic threads that are terminated at one end with pyridyl groups. These rotaxanes can be coordinated to [Cu(hfac)2] (where Hhfac = 1,1,1,5,5,5-hexafluoroacetylacetone), to give 1:1 or 1:2 Cu:{Cr7Ni} adducts: {[Cu(hfac)2](py-CH2NH2CH2CH2Ph)[Cr7NiF8(O2C t Bu)16]}, {[Cu(hfac)2][py-CH2NH2CH2CH3][Cr7NiF8(O2C t Bu)16]}, {[Cu(hfac)2]([py-CH2CH2NH2CH2C6H4SCH3][Cr7NiF8(O2C t Bu)16])2}, {[Cu(hfac)2]([py-C6H4-CH2NH2(CH2)4Ph][Cr7NiF8(O2C t Bu)16])2}, and {[Cu(hfac)2]([3-py-CH2CH2NH2(CH2)3SCH3][Cr7NiF8(O2C t Bu)16])2}, the structures of which have been determined by X-ray diffraction. The {Cr7Ni} rings and CuII ions both have electronic spin S = 1/2, but with very different g-values. Continuous-wave EPR spectroscopy reveals the exchange interactions between these dissimilar spins, and hence the communication between the different molecular components that comprise these supramolecular systems. The interactions are weak such that we observe AX or AX2 type spectra. The connectivity between the {Cr7Ni} ring and thread terminus is varied such that the magnitude of the exchange interaction J can be tuned. The coupling is shown to be dominated by through-bond rather than through-space mechanisms.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | 03 Chemical Sciences |
| Subjects: | Q Science > QD Chemistry Q Science > QH Natural history > QH301 Biology |
| Divisions: | Pharmacy & Biomolecular Sciences |
| Publisher: | American Chemical Society |
| Related URLs: | |
| Date Deposited: | 21 Oct 2019 09:46 |
| Last Modified: | 04 Sep 2021 08:37 |
| DOI or ID number: | 10.1021/jacs.9b05590 |
| URI: | https://researchonline.ljmu.ac.uk/id/eprint/11612 |
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