Anion binding by a tetradipicolylamine-substituted resorcinarene cavitand

Joseph S. Gardner, Martin Conda Sheridan, Dana N. Smith, Roger G. Harrison, John D. Lamb

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Anion binding has been achieved with a resorcinarene substituted with four 2,2′-dipicolylamine moieties on the upper rim. The four dipicolylamine groups reside in proximity on one rim of the cavitand. The dipicolylamine groups were protonated with triflic acid to provide the cationic ammonium sites for anion binding. This anion receptor binds strongly to anions of different geometries, such as H 2PO 4 -, Cl -, F -, CH 3CO 2 -, HSO 4 -, and NO 3 -. The association constants for binding these anions are large, on the order of log K = 5 in CD 3CN, a solvent of intermediate dielectric constant. These values represent significant binding compared to other cavitands with nitrogen pendant groups. Evidence suggests that the cavitand provides two identical receptor sites formed by two dipicolylamine groups, facilitating the simultaneous binding of two anions. Intramolecular binding of anions between two protonated dipicolylamine groups is indicated on the basis of the comparison to a structurally similar monomeric analogue and by semiempirical PM3 molecular modeling. Titrations with the analogue result in much weaker anion association, even at high concentrations, indicating the importance of proximity and preorganization of sites on the cavitand upper rim.

Original languageEnglish (US)
Pages (from-to)4295-4300
Number of pages6
JournalInorganic Chemistry
Volume44
Issue number12
DOIs
StatePublished - Jun 13 2005

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Anions
anions
rims
proximity
Association reactions
analogs
Molecular modeling
cavitand
resorcinarene
Titration
Ammonium Compounds
titration
Permittivity
Nitrogen
2,2'-dipicolylamine
methylidyne
permittivity
nitrogen
acids
Geometry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Anion binding by a tetradipicolylamine-substituted resorcinarene cavitand. / Gardner, Joseph S.; Conda Sheridan, Martin; Smith, Dana N.; Harrison, Roger G.; Lamb, John D.

In: Inorganic Chemistry, Vol. 44, No. 12, 13.06.2005, p. 4295-4300.

Research output: Contribution to journalArticle

Gardner, Joseph S. ; Conda Sheridan, Martin ; Smith, Dana N. ; Harrison, Roger G. ; Lamb, John D. / Anion binding by a tetradipicolylamine-substituted resorcinarene cavitand. In: Inorganic Chemistry. 2005 ; Vol. 44, No. 12. pp. 4295-4300.
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