title: High binding yet accelerated guest rotation within a cucurbit[7]uril complex. Toward paramagnetic gyroscopes and rolling nanomachines.
abstract: The (15-oxo-3,7,11-triazadispiro[5.1.5.3]hexadec-7-yl)oxidanyl, a bis-spiropiperidinium nitroxide derived from TEMPONE, can be included in cucurbit[7]uril to form a strong (K(a)∼ 2 × 10(5) M(-1)) CB[7]@bPTO complex. EPR and MS spectra, DFT calculations, and unparalleled increased resistance (a factor of ∼10(3)) toward ascorbic acid reduction show evidence of deep inclusion of bPTO inside CB[7]. The unusual shape of the CB[7]@bPTO EPR spectrum can be explained by an anisotropic Brownian rotational diffusion, the global tumbling of the complex being slower than rotation of bPTO around its "long molecular axis" inside CB[7]. The CB[7] (stator) with the encapsulated bPTO (rotator) behaves as a supramolecular paramagnetic rotor with increased rotational speed of the rotator that has great potential for advanced nanoscale machines requiring wheels such as cucurbiturils with virtually no friction between the wheel and the axle for optimum wheel rotation (i.e. nanopulleys and nanocars).
authors.affiliation: Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, UMR 7273, 13013 Marseille, France. david.bardelang@univ-amu.fr paul.tordo@univ-amu.fr olivier.ouari@univ-amu.fr.
authors.forename: G
authors.initials: G
authors.lastname: Casano
authors.forename: F
authors.initials: F
authors.lastname: Poulhès
authors.forename: T K
authors.initials: TK
authors.lastname: Tran
authors.forename: M M
authors.initials: MM
authors.lastname: Ayhan
authors.forename: H
authors.initials: H
authors.lastname: Karoui
authors.forename: D
authors.initials: D
authors.lastname: Siri
authors.forename: A
authors.initials: A
authors.lastname: Gaudel-Siri
authors.forename: A
authors.initials: A
authors.lastname: Rockenbauer
authors.forename: G
authors.initials: G
authors.lastname: Jeschke
authors.forename: D
authors.initials: D
authors.lastname: Bardelang
authors.forename: P
authors.initials: P
authors.lastname: Tordo
authors.forename: O
authors.initials: O
authors.lastname: Ouari