A conformationally flexible, urea-based tripodal anion receptor: Solid-state, solution, and theoretical studies

D R Turner, Martin Paterson, J W Steed

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150 Citations (Scopus)

Abstract

Tripodal tris(urea) cationic receptors 1 and 2 containing p-tolyl or octyl substituents, respectively, have been synthesized, and their association behavior with anionic guests has been studied via a variety of methods. The receptors are based around a hexasubstituted aryl core and contain both urea and pyridinium functionalities. For 1: 1 complexes, anions reside within the central cavity of the host species, held by hydrogen bonds from both NH and CH donors. The following host-anion complexes have been characterized by X-ray crystallography: 1-(Br)(3), 1-(PF6)(3)center dot 2(CH3)(2)CO, and 1-(NO3)(1.5)(PF6)(1.5). Each structure contains the receptor in a significantly different geometry, highlighting the anion-dependent conformational flexibility of 1. Solution H-1 NMR spectroscopic titrations have shown the two host species to display significant affinity for both halides and hydrogen sulfate and strongly suggest the persistence of CH center dot center dot center dot X- interactions despite the presence of "stronger" NH donor groups. Variable-temperature H-1 NMR studies on the more soluble octyl derivative 2 show that there is a distinct change in conformation associated with the formation of a 1: 1 host/guest complex. Computations using density functional theory (with the B3LYP functional) have been employed to aid in understanding the geometry of the 1:1 host/chloride complexes of 1 and 2. These experiments suggest that the lowest energy conformation for 1-Cl is one in which the ureidopyridinium arms are orientated upward forming a cavity that is sealed by CH center dot center dot center dot pi interactions, effectively forming a unimolecular capsule, whereas for 2 a less symmetrical "2-up, 1-down" geometry is favored.

Original languageEnglish
Pages (from-to)1598-1608
Number of pages11
JournalJournal of Organic Chemistry
Volume71
Issue number4
DOIs
Publication statusPublished - 17 Feb 2006

Keywords

  • HYDROGEN-BONDS
  • SYNTHETIC RECEPTOR
  • ORGANIC FLUORINE
  • ARTIFICIAL RECEPTORS
  • IMIDAZOLIUM RECEPTOR
  • CRYSTAL-STRUCTURES
  • NEUTRAL RECEPTORS
  • BINDING
  • RECOGNITION
  • COMPLEXES

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