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Modular Synthesis and Dynamics of a Variety of Donor–Acceptor Interlocked Compounds Prepared by Click Chemistry

  1. Adam B. Braunschweig Dr.1,3,
  2. William R. Dichtel Dr.1,2,
  3. Ognjen Š. Miljanić Dr.1,
  4. Mark A. Olson1,
  5. Jason M. Spruell1,
  6. Saeed I. Khan Dr.1,
  7. James R. Heath Prof. Dr.2,
  8. J. Fraser Stoddart Prof. Dr.1

Article first published online: 27 APR 2007

DOI: 10.1002/asia.200700035

Issue

Chemistry – An Asian Journal

Chemistry – An Asian Journal

Volume 2, Issue 5, pages 634–647, May 4, 2007

Additional Information

How to Cite

Braunschweig, A., Dichtel, W., Miljanić, O., Olson, M., Spruell, J., Khan, S., Heath, J. and Stoddart, J. (2007), Modular Synthesis and Dynamics of a Variety of Donor–Acceptor Interlocked Compounds Prepared by Click Chemistry. Chemistry – An Asian Journal, 2: 634–647. doi: 10.1002/asia.200700035

Author Information

  1. 1

    The California NanoSystems Institute and Department of Chemistry and Biochemistry, University of California, Los Angeles, 405 Hilgard Avenue, Los Angeles, CA 90095, USA, Fax: (+1) 310-206-5621

  2. 2

    Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, Pasadena, CA 91125, USA, Tel: (+1) 626-395-8920

  3. 3

    Current Address: Institute of Chemistry and the Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 92101, Israel

Publication History

  1. Issue published online: 27 APR 2007
  2. Article first published online: 27 APR 2007
  3. Manuscript Received: 1 FEB 2007

Funded by

  • Microelectronics Advanced Research Corporation
  • Focus Centers on Functional Engineered Nanoarchitectonics
  • Materials Structures and Devices, the Moletronics Program
  • Defense Advanced Research Projects Agency
  • DARPA
  • Center for Nanoscale Innovation for Defense
  • NSF

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Keywords:

  • click chemistry;
  • cycloaddition;
  • host–guest systems;
  • interlocked compounds;
  • rotaxanes

Graphical Abstract

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Clicking into position: Donor–acceptor rotaxanes can be synthesized by a threading-followed-by-stoppering approach, in which the required stoppers are attached to the precursor pseudorotaxanes by CuI-catalyzed Huisgen 1,3-dipolar cycloaddition. This approach to rotaxanes with a donor 1,5-dioxynaphthalene unit and a cyclophane acceptor gives higher yields than conventional strategies.

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 CuI-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.

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