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Title: Translational isomerism and dynamics in multi-hydroquinone derived porphyrin [2]- and [3]-catenanes
Contributor(s): Gunter, Maxwell John (author); Farquhar, Sandra (author); Jeynes, Tyrone (author)
Publication Date: 2003
DOI: 10.1039/b308157e
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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 [2] and [3]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 [2]- and [3]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 [3]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
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