Interlocked Host Anion Recognition by an Indolocarbazole-Containing [2]Rotaxane
authors Brown, A; Mullen, KM; Ryu, J; Chmielewski, MJ; Santos, SM; Felix, V; Thompson, AL; Warren, JE; Pascu, SI; Beer, PD
nationality International
journal JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
keywords HYDROGEN-BONDING INTERACTIONS; NEUTRAL MACROCYCLIC AMIDES; INDOLE-BASED MACROCYCLES; X-RAY-DIFFRACTION; MOLECULAR MECCANO; DIHYDROGEN PHOSPHATE; ORGANIC-SOLVENTS; AQUEOUS-SOLUTION; CLICK CHEMISTRY; BINDING AGENTS
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. H-1 NMR and UV-visible spectroscopies and X-ray crystallography demonstrated the importance of pi-donor-acceptor, CH center dot center dot center dot pi, and electrostatic interactions in the assembly of pseudorotaxanes between the electron-deficient tetracationic macrocycle and a series of pi-electron-rich indolocarbazole derivatives. Subsequent urethane stoppering of one of these complexes afforded a [2]rotaxane, which was shown by H-1 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.
publisher AMER CHEMICAL SOC
issn 0002-7863
year published 2009
volume 131
issue 13
beginning page 4937
ending page 4952
digital object identifier (doi) 10.1021/ja809905x
web of science category Chemistry, Multidisciplinary
subject category Chemistry
unique article identifier WOS:000264806300069
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journal impact factor 14.612
5 year journal impact factor 14.549
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