title: Gated electron sharing within dynamic naphthalene diimide-based oligorotaxanes.
abstract: The controlled self-assembly of well-defined and spatially ordered π-systems has attracted considerable interest because of their potential applications in organic electronics. An important contemporary pursuit relates to the investigation of charge transport across noncovalently coupled components in a stepwise fashion. Dynamic oligorotaxanes, prepared by template-directed methods, provide a scaffold for directing the construction of monodisperse one-dimensional assemblies in which the functional units communicate electronically through-space by way of π-orbital interactions. Reported herein is a series of oligorotaxanes containing one, two, three and four naphthalene diimide (NDI) redox-active units, which have been shown by cyclic voltammetry, and by EPR and ENDOR spectroscopies, to share electrons across the NDI stacks. Thermally driven motions between the neighboring NDI units in the oligorotaxanes influence the passage of electrons through the NDI stacks in a manner reminiscent of the conformationally gated charge transfer observed in DNA.
authors.affiliation: Center for the Chemistry of Integrated Systems (CCIS) and Argonne-Northwestern Solar Energy Research (ANSER) Center, Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208 (USA) http://chemgroups.northwestern.edu/wasielewski http://stoddart.northwestern.edu.
authors.forename: Alyssa-Jennifer
authors.initials: AJ
authors.lastname: Avestro
authors.forename: Daniel M
authors.initials: DM
authors.lastname: Gardner
authors.forename: Nicolaas A
authors.initials: NA
authors.lastname: Vermeulen
authors.forename: Eleanor A
authors.initials: EA
authors.lastname: Wilson
authors.forename: Severin T
authors.initials: ST
authors.lastname: Schneebeli
authors.forename: Adam C
authors.initials: AC
authors.lastname: Whalley
authors.forename: Matthew E
authors.initials: ME
authors.lastname: Belowich
authors.forename: Raanan
authors.initials: R
authors.lastname: Carmieli
authors.forename: Michael R
authors.initials: MR
authors.lastname: Wasielewski
authors.forename: J Fraser
authors.initials: JF
authors.lastname: Stoddart
mesh_terms: D002384:Catalysis; D004578:Electron Spin Resonance Spectroscopy; D004583:Electrons; D006860:Hydrogen Bonding; D007094:Imides / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009281:Naphthalenes / Q000737:chemistry*; D043862:Rotaxanes / Q000737:chemistry*
chemical_list: D007094:Imides; D009281:Naphthalenes; D043862:Rotaxanes; C542131:naphthalenediimide
keywords: electron transport; mechanically interlocked molecules; radical anions; self-assembly; template-directed synthesis