Interlocked host anion recognition by an indolocarbazole-containing [2]rotaxane

A Brown, K M Mullen, J Ryu, M J Chmielewski, S M Santos, V Felix, A L Thompson, John E Warren, Sofia I Pascu, P D Beer

Research output: Contribution to journalArticle

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Abstract

The design, synthesis, structure, and anion-binding properties of the first indolocarbazole-containing interlocked structure are described. The novel [2]rotaxane molecular structure incorporates a neutral indolocarbazole-containing axle component which is encircled by a tetracationic macrocycle functionalized with an isophthalamide anion recognition motif. 1H NMR and UV−visible spectroscopies and X-ray crystallography demonstrated the importance of π-donor−acceptor, CH···π, and electrostatic interactions in the assembly of pseudorotaxanes between the electron-deficient tetracationic macrocycle and a series of π-electron-rich indolocarbazole derivatives. Subsequent urethane stoppering of one of these complexes afforded a [2]rotaxane, which was shown by 1H NMR spectroscopic titration experiments to exhibit enhanced chloride and bromide anion recognition compared to its non-interlocked components. Computational molecular dynamics simulations provide further insight into the mechanism and structural nature of the anion recognition process, confirming it to involve cooperative hydrogen-bond donation from both macrocycle and indolocarbazole components of the rotaxane. The observed selectivity of the [2]rotaxane for chloride is interpreted in terms of its unique interlocked binding cavity, defined by the macrocycle isophthalamide and indolocarbazole N−H protons, which is complementary in size and shape to this halide guest.
Original languageEnglish
Pages (from-to)4937-4952
Number of pages16
JournalJournal of the American Chemical Society
Volume131
Issue number13
Early online date18 Mar 2009
DOIs
Publication statusPublished - 8 Apr 2009

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Rotaxanes
Anions
Negative ions
Nuclear magnetic resonance
Chlorides
Electrons
X ray crystallography
Axles
Coulomb interactions
Titration
Molecular structure
X Ray Crystallography
Urethane
Molecular dynamics
Molecular Dynamics Simulation
Hydrogen bonds
Protons
Molecular Structure
Static Electricity
Bromides

Cite this

Brown, A., Mullen, K. M., Ryu, J., Chmielewski, M. J., Santos, S. M., Felix, V., ... Beer, P. D. (2009). Interlocked host anion recognition by an indolocarbazole-containing [2]rotaxane. Journal of the American Chemical Society, 131(13), 4937-4952. https://doi.org/10.1021/ja809905x

Interlocked host anion recognition by an indolocarbazole-containing [2]rotaxane. / Brown, A; Mullen, K M; Ryu, J; Chmielewski, M J; Santos, S M; Felix, V; Thompson, A L; Warren, John E; Pascu, Sofia I; Beer, P D.

In: Journal of the American Chemical Society, Vol. 131, No. 13, 08.04.2009, p. 4937-4952.

Research output: Contribution to journalArticle

Brown, A, Mullen, KM, Ryu, J, Chmielewski, MJ, Santos, SM, Felix, V, Thompson, AL, Warren, JE, Pascu, SI & Beer, PD 2009, 'Interlocked host anion recognition by an indolocarbazole-containing [2]rotaxane', Journal of the American Chemical Society, vol. 131, no. 13, pp. 4937-4952. https://doi.org/10.1021/ja809905x
Brown A, Mullen KM, Ryu J, Chmielewski MJ, Santos SM, Felix V et al. Interlocked host anion recognition by an indolocarbazole-containing [2]rotaxane. Journal of the American Chemical Society. 2009 Apr 8;131(13):4937-4952. https://doi.org/10.1021/ja809905x
Brown, A ; Mullen, K M ; Ryu, J ; Chmielewski, M J ; Santos, S M ; Felix, V ; Thompson, A L ; Warren, John E ; Pascu, Sofia I ; Beer, P D. / Interlocked host anion recognition by an indolocarbazole-containing [2]rotaxane. In: Journal of the American Chemical Society. 2009 ; Vol. 131, No. 13. pp. 4937-4952.
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