Redox-Controllable Amphiphilic [2]Rotaxanes

Hsian Rong Tseng, Scott A. Vignon, Paul C. Celestre, Julie Perkins, Jan O. Jeppesen, Alberto Di Fabio, Roberto Ballardini, M. Teresa Gandolfi*, Margherita Venturi, Vincenzo Balzani, J. Fraser Stoddart

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

149 Scopus citations

Abstract

With the fabrication of molecular electronic devices (MEDs) and the construction of nanoelectromechanical systems (NEMSs) as incentives, two constitutionally isomeric, redox-controllable [2]rotaxanes have been synthesized and characterized in solution. Therein, they both behave as near-perfect molecular switches, that is, to all intents and purposes, these two rotaxanes can be switched precisely by applying appropriate redox stimuli between two distinct chemomechanical states. Their dumbbell-shaped components are composed of polyether chains interrupted along their lengths by i) two π-electron rich recognition sites-a tetrathiafulvalene (TTF) unit and a 1,5-dioxynaphthalene (DNP) moiety-with ii) a rigid terphenylene spacer placed between the two recognition sites, and then terminated by iii) a hydrophobic tetraarylmethane stopper at one end and a hydrophilic dendritic stopper at the other end of the dumbbells, thus conferring amphiphilicity upon these molecules. A template-directed protocol produces a means to introduce the tetracationic cyclophane, cyclobis(paraquat-p-phenylene) (CBPQT4+), which contains two π-electron accepting bipyridinium units, mechanically interlocked around the dumbbell-shaped components. Both the TTF unit and the DNP moiety are potential stations for CBPQT4+, since they can establish charge-transfer and hydrogen bonding interactions with the bipyridinium units of the cyclophane, thereby introducing bistability into the [2]rotaxanes. In both constitutional isomers, 1H NMR and absorption spectroscopies, together with electrochemical investigations, reveal that the CBPOT 4+ ring is predominantly located on the TTF unit, leading to the existence of a single translational isomer (co-conformation) in both cases. In addition, a model [2]rotaxane, incorporating hydrophobic tetraarylmethane stoppers at both ends of its dumbbell-shaped component, has also been synthesized as a point of reference. Molecular synthetic approaches were used to construct convergently the dumbbell-shaped compounds by assembling progressively smaller building blocks in the shape of the rigid spacer, the TTF unit and the DNP moiety, and the hydrophobic and hydrophilic stoppers. The two amphiphilic bistable [2]rotaxanes are constitutional isomers in the sense that, in one constitution, the TTF unit is adjacent to the hydrophobic stopper, whereas in the other, it is next to the hydrophilic stopper. All three bistable [2]rotaxanes have been isolated as green solids. Electrospray and fast atom bombardment mass spectra support the gross structural assignments given to all three of these mechanically interlocked compounds. Their photophysical and electrochemical properties have been investigated in acetonitrile. The results obtained from these investigations confirm that, in all three [2]rotaxanes, i) the CBPQT4+ cyclophane encircles the TTF unit, ii) the CBPQT 4+ cyclophane shuttles between the TTF and DNP stations upon electrochemical or chemical oxidation/reduction of the TTF unit, and iii) folded conformations are present in which the CBPQT4+ cyclophane, while encircling the TTF unit, interacts through its π-accepting bipyridinium exteriors with other π-donating components of the dumbbells, especially those located within the stoppers.

Original languageEnglish (US)
Pages (from-to)155-172
Number of pages18
JournalChemistry - A European Journal
Volume10
Issue number1
DOIs
StatePublished - Jan 5 2004

Keywords

  • Molecular shuttle
  • Nanoscale switches
  • Redox processes
  • Self-assembly
  • Template-directed synthesis
  • Tetrathiafulvalene

ASJC Scopus subject areas

  • Chemistry(all)

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