title: Facile method for preparing surface-mounted cucurbit[8]uril-based rotaxanes.
abstract: Surface-immobilized rotaxanes are of practical interest for myriad applications including molecular rotors and analytical sensing. Herein, we present a facile method for the preparation of cucurbit[8]uril (CB[8])-based rotaxanes on gold (Au) surfaces threaded onto a viologen (MV(2+)) axle. The surface-bound CB[8] rotaxanes were characterized by contact angle measurements and optical microscopy. Direct imaging of the rotaxanes was accomplished by attaching either azobenzene-functionalized silica (Si-azo) colloids or fluorescein-labeled dopamine that were bound to the Au surface through a supramolecular heteroternary (1:1:1) complex with CB[8]. The surface density of CB[8] rotaxanes was examined based on their detection of dopamine. The calculated surface density is 4.8 × 10(13) molecules·cm(-2), which is only slightly lower than the theoretical value of 5.0 × 10(13) molecules·cm(-2). Surface-functionalized rotaxanes can be reversibly switched using external stimuli to bind electron-rich second guests for CB[8], including both small molecules such as dopamine and appropriately-functionalized colloidal particles. Such controlled reversibility gives rise to potential applications including selective sensing or reusable templates for preparing well-defined colloidal arrays. The formation of the surface-bound rotaxane structure is critical for successfully anchoring CB[8] host molecules onto Au substrates, yielding an interlocked architecture and preventing the dissociation of binary host-guest complex MV(2+)⊂CB[8]. The MV(2+)⊂CB[8] rotaxane structure thus effectively maintains the material density on the Au surface and dramatically enhances the stability of the functional surface.
authors.affiliation: Melville Laboratory for Polymer Synthesis, Department of Chemistry, University of Cambridge , Cambridge CB2 1EW, United Kingdom.
authors.forename: Chi
authors.initials: C
authors.lastname: Hu
authors.forename: Yang
authors.initials: Y
authors.lastname: Lan
authors.forename: Feng
authors.initials: F
authors.lastname: Tian
authors.forename: Kevin R
authors.initials: KR
authors.lastname: West
authors.forename: Oren A
authors.initials: OA
authors.lastname: Scherman