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|Title:||Translational isomerism and dynamics in multi-hydroquinone derived porphyrin - and -catenanes||Contributor(s):||Gunter, Maxwell John (author); Farquhar, Sandra (author); Jeynes, Tyrone (author)||Publication Date:||2003||DOI:||10.1039/b308157e||Handle Link:||https://hdl.handle.net/1959.11/1475||Abstract:||A series of porphyrins strapped with polyether chains containing two or three 1,4-dioxybenzene units has been synthesised with a view to the production of porphyrin-containing  and catenanes, where the porphyrin is strapped between ortho-positions of 5,15-(meso)-diaryl groups, and is interlinked with the bipyridinium macrocyclecyclobis(paraquat-4,4'-biphenylene). The porphyrins were isolated as mixtures of atropisomers, where the linking strap spans across the face of the porphyrin (α,α-isomer), or 'twisted' around its side (α,β-isomer). Their structures were determined by detailed ¹H NMR spectroscopy. The bis-1,4-dioxybenzene-strapped derivatives were shown to undergo atropisomerisation on heating, to produce an equilibrium mixture. Catenation under high pressure conditions of the mixture, or of the individual isomers, produced only a single catenane, that of the α,α-isomer.Its structure was determined by mass spectral and dynamic NMR measurements. Rates were determined for:(i) translational motion or 'shuttling' between 1,4-dioxybenzenes; (ii) 'rotation' of the macrocycle around the1,4-dioxybenzene axis; and (iii) 'rocking' of the 1,4-dioxybenzene within the macrocycle. The atropisomers of the strapped derivatives containing three 1,4-dioxybenzene units were also separated, and subjected to catenation.Both - and catenanes were isolated, and were shown to be stable to further atropisomerisation. Their solution structures were probed in detail by dynamic ¹H NMR measurements. The rates for shuttling and rotation were obtained in certain cases, although the complexity of the spectra of the catenanes prevented a more detailed investigation.||Publication Type:||Journal Article||Source of Publication:||Organic & Biomolecular Chemistry, 1(0), p. 4097-4112||Publisher:||Royal Society of Chemistry||Place of Publication:||Cambridge, England||ISSN:||1477-0520||Field of Research (FOR):||030302 Nanochemistry and Supramolecular Chemistry||Peer Reviewed:||Yes||HERDC Category Description:||C1 Refereed Article in a Scholarly Journal||Statistics to Oct 2018:||Visitors: 112
|Appears in Collections:||Journal Article|
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