Controllable donor-acceptor neutral [2]rotaxanes

Takahiro Iijima, Scott A. Vignon, Hsian Rong Tseng, Thibaut Jarrosson, Jeremy K M Sanders, Filippo Marchioni, Margherita Venturi, Emanuela Apostoli, Vincenzo Balzani, J. Fraser Stoddart

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Abstract

In pursuit of a neutral bistable [2]rotaxane made up of two tetraarylmethane stoppers - both carrying one isopropyl and two tert-butyl groups located at the para positions on each of three of the four aryl rings - known to permit the slippage of the π-electron-donating 1,5-dinaphtho[38] crown-10 (1/5DNP38C10) at the thermodynamic instigation of π-electron- accepting recognition sites, in this case, pyromellitic diimide (PmI) and 1,4,5,8-naphthalene-tetracarboxylate diimide (NpI) units separated from each other along the rod section of the rotaxane's dumbbell component, and from the para positions of the fourth aryl group of the two stoppers by pentamethylene chains, a modular approach was employed in the synthesis of the dumbbell-shaped compound NpPmD, as well as of its two degenerate counterparts, one (PmPmD) which contains two PmI units and the other (NpNpD) which contains two NpI units. The bistable [2]rotaxane NpPmR, as well as its two degenerate analogues PmPmR and NpNpR, were obtained from the corresponding dumbbell-shaped compounds NpPmD, PmPmD, and NpNpD and 1/5DNP38C10 by slippage. Dynamic 1H NMR spectroscopy in CD2Cl2 revealed that shuttling of the 1/5DNP38C10 ring occurs in NpNpR and PmPmR, with activation barriers of 277 K of 14.0 and 10.9 kcal mol-1, respectively, reflecting a much more pronounced donor-acceptor stabilizing interaction involving the NpI units over the PmI ones. The photophysical and electrochemical properties of the three neutral [2]rotaxanes and their dumbbell-shaped precursors have also been investigated in CH2Cl2. Interactions between 1/5DNP38C10 and PmI and NpI units located within the rod section of the dumbbell components of the [2]rotaxane give rise to the appearance of charge-transfer bands, the energies of which correlate with the electron-accepting properties of the two diimide moieties. Comparison between the positions of the visible absorption bands in the three [2]rotaxanes shows that, in NpPmR, the major translational isomer is the one in which 1/5DNP38C10 encircles the NpI unit. Correlations of the reduction potentials for all the compounds studied confirm that, in this non-degenerate [2]rotaxane, one of the translational isomers predominates. Furthermore, after deactivation of the NpI unit by one-electron reduction, the 1/5DNP38C10 macrocycle moves to the PmI unit. Li+ ions have been found to strengthen the interaction between the electron-donating crown ether and the electron-accepting diimide units, particularly the PmI one. Titration experiments show that two Li+ ions are involved in the strengthening of the donor-acceptor interaction. Addition of Li+ ions to NpPmR induces the 1/5DNP38C10 macrocycle to move from the NpI to the PmI unit. The Li+-ion-promoted switching of NpPmR in a 4:1 mixture of CD 2Cl2 and CD3COCD3 has also been shown by 1H NMR spectroscopy to involve the mechanical movement of the 1/5DNP38C10 macrocycle from the NpI to the PmI unit, a process that can be reversed by adding an excess of [12]crown-4 to sequester the Li+ ions.

Original languageEnglish (US)
Pages (from-to)6375-6392
Number of pages18
JournalChemistry - A European Journal
Volume10
Issue number24
DOIs
StatePublished - Dec 3 2004

Keywords

  • Bistable switches
  • Molecular devices
  • Rotaxanes
  • Self-assembly
  • Template synthesis

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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