title: Modular synthesis and dynamics of a variety of donor-acceptor interlocked compounds prepared by click chemistry.
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 pi-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 pi-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.
authors.affiliation: The California NanoSystems Institute and Department of Chemistry and Biochemistry, University of California, Los Angeles, 405 Hilgard Avenue, Los Angeles, CA 90095, USA.
authors.forename: Adam B
authors.initials: AB
authors.lastname: Braunschweig
authors.forename: William R
authors.initials: WR
authors.lastname: Dichtel
authors.forename: Ognjen S
authors.initials: OS
authors.lastname: Miljanić
authors.forename: Mark A
authors.initials: MA
authors.lastname: Olson
authors.forename: Jason M
authors.initials: JM
authors.lastname: Spruell
authors.forename: Saeed I
authors.initials: SI
authors.lastname: Khan
authors.forename: James R
authors.initials: JR
authors.lastname: Heath
authors.forename: J Fraser
authors.initials: JF
authors.lastname: Stoddart