Modular synthesis and dynamics of a variety of donor-acceptor interlocked compounds prepared by click chemistry

Adam Braunschweig, William R. Dichtel, Ognjen Š Miljanić, Mark A. Olson, Jason M. Spruell, Saeed I. Khan, James R. Heath, J. Fraser Stoddart

Research output: Contribution to journalArticle

82 Citations (Scopus)

Abstract

A series of donor-acceptor [2]-, [3]-, and [4]rotaxanes and self-complexes ([1]rotaxanes) have been synthesized by a threading-followed-by-stoppering approach, in which the precursor pseudorotaxanes are fixed by using Cu I-catalyzed Huisgen 1,3-dipolar cycloaddition to attach the required stoppers. This alternative approach to forming rotaxanes of the donor-acceptor type, in which the donor is a 1,5-dioxynaphthalene unit and the acceptor is the tetracationic cyclophane cyclobis(paraquat-p-phenylene), proceeds with enhanced yields relative to the tried and tested synthetic strategies, which involve the clipping of the cyclophane around a preformed dumbbell containing π-electron-donating recognition sites. The new synthetic approach is amenable to application to highly convergent sequences. To extend the scope of this reaction, we constructed [2]rotaxanes in which one of the phenylene rings of the tetracationic cyclophane is perfluorinated, a feature which significantly weakens its association with π-electron-rich guests. The activation barrier for the shuttling of the cyclophane over a spacer containing two triazole rings was determined to be (15.5 ± 0.1) kcal mol-1 for a degenerate two-station [2]rotaxane, a value similar to that previously measured for analogous degenerate compounds containing aromatic or ethylene glycol spacers. The triazole rings do not seem to perturb the shuttling process significantly; this property bodes well for their future incorporation into bistable molecular switches.

Original languageEnglish (US)
Pages (from-to)634-647
Number of pages14
JournalChemistry - An Asian Journal
Volume2
Issue number5
DOIs
StatePublished - 2007
Externally publishedYes

Fingerprint

Rotaxanes
Click Chemistry
Triazoles
Electrons
Paraquat
Cycloaddition
Ethylene Glycol
Cycloaddition Reaction
Chemical activation
Switches
Association reactions

Keywords

  • Click chemistry
  • Cycloaddition
  • Host-guest systems
  • Interlocked compounds
  • Rotaxanes

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Braunschweig, A., Dichtel, W. R., Miljanić, O. Š., Olson, M. A., Spruell, J. M., Khan, S. I., ... Stoddart, J. F. (2007). Modular synthesis and dynamics of a variety of donor-acceptor interlocked compounds prepared by click chemistry. Chemistry - An Asian Journal, 2(5), 634-647. https://doi.org/10.1002/asia.200700035

Modular synthesis and dynamics of a variety of donor-acceptor interlocked compounds prepared by click chemistry. / Braunschweig, Adam; Dichtel, William R.; Miljanić, Ognjen Š; Olson, Mark A.; Spruell, Jason M.; Khan, Saeed I.; Heath, James R.; Stoddart, J. Fraser.

In: Chemistry - An Asian Journal, Vol. 2, No. 5, 2007, p. 634-647.

Research output: Contribution to journalArticle

Braunschweig, A, Dichtel, WR, Miljanić, OŠ, Olson, MA, Spruell, JM, Khan, SI, Heath, JR & Stoddart, JF 2007, 'Modular synthesis and dynamics of a variety of donor-acceptor interlocked compounds prepared by click chemistry', Chemistry - An Asian Journal, vol. 2, no. 5, pp. 634-647. https://doi.org/10.1002/asia.200700035
Braunschweig, Adam ; Dichtel, William R. ; Miljanić, Ognjen Š ; Olson, Mark A. ; Spruell, Jason M. ; Khan, Saeed I. ; Heath, James R. ; Stoddart, J. Fraser. / Modular synthesis and dynamics of a variety of donor-acceptor interlocked compounds prepared by click chemistry. In: Chemistry - An Asian Journal. 2007 ; Vol. 2, No. 5. pp. 634-647.
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