title: 1,3-Alternate Tetraamido-Azacalix[4]arenes as Selective Anion Receptors.
abstract: Six tetraaza[1.1.1.1]cyclophane derivatives bearing peripheral amide groups were prepared according to two distinct synthetic strategies that depend on the connection pattern between the aryl units. NMR experiments combined with the X-ray structures of two tetraamide derivatives 4 b and 10 show that these cavitands adopt a 1,3-alternate conformation both in solution and in the solid state. Consequently, the four amide groups of the aza[1.1.1.1]-m,m,m,m-cyclophane isomer 10 can contribute to the same recognition process towards neutral water molecules or anion guests. NMR experiments, mass spectrometry analyses and single-crystal X-ray structures confirm the anion-binding ability of this receptor. Absorption spectrophotometric titrations in nonpolar solvents provided evidence for the selectivity of 10 to chloride anions in the halide series, with a corresponding association constant Ka reaching 2.5 × 10(6) m(-1).
authors.affiliation: Centre Interdisciplinaire de Nanosciences de Marseille (CINaM), Aix Marseille Université, CNRS UMR 7325, 13288, Marseille, France), Fax. gabriel.canard@univ-amu.fr.
authors.forename: Gabriel
authors.identifier: http://orcid.org/0000-0002-3572-9091
authors.initials: G
authors.lastname: Canard
authors.affiliation: Centre Interdisciplinaire de Nanosciences de Marseille (CINaM), Aix Marseille Université, CNRS UMR 7325, 13288, Marseille, France), Fax.
authors.forename: Judicaelle Andeme
authors.initials: JA
authors.lastname: Edzang
authors.affiliation: Centre Interdisciplinaire de Nanosciences de Marseille (CINaM), Aix Marseille Université, CNRS UMR 7325, 13288, Marseille, France), Fax.
authors.forename: Zhongrui
authors.initials: Z
authors.lastname: Chen
authors.affiliation: Laboratoire de Chimie Bioorganique et Médicinale, UMR 7509 CNRS-, Université de Strasbourg, ECPM, 25 rue Becquerel, 67087, Strasbourg Cedex, France.
authors.forename: Matthieu
authors.initials: M
authors.lastname: Chessé
authors.affiliation: Laboratoire de Chimie Bioorganique et Médicinale, UMR 7509 CNRS-, Université de Strasbourg, ECPM, 25 rue Becquerel, 67087, Strasbourg Cedex, France.
authors.forename: Mourad
authors.initials: M
authors.lastname: Elhabiri
authors.affiliation: Fédération des Sciences Chimiques de Marseille-Spectropole FR 1739, Aix Marseille Université, 13397, Marseille, France.
authors.forename: Michel
authors.initials: M
authors.lastname: Giorgi
authors.affiliation: Centre Interdisciplinaire de Nanosciences de Marseille (CINaM), Aix Marseille Université, CNRS UMR 7325, 13288, Marseille, France), Fax. olivier.siri@univ-amu.fr.
authors.forename: Olivier
authors.initials: O
authors.lastname: Siri
mesh_terms: D000838:Anions / Q000737:chemistry*; D001372:Aza Compounds / Q000737:chemistry*; D047250:Calixarenes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D015394:Molecular Structure; D012997:Solvents / Q000737:chemistry; D000097566:Cyclophanes
chemical_list: D000838:Anions; D001372:Aza Compounds; D047250:Calixarenes; D006571:Heterocyclic Compounds; D012997:Solvents; C000610131:tetraaza(1.1.1.1)cyclophane; D000097566:Cyclophanes
keywords: anions; calixarenes; conformation analysis; host-guest systems; macrocycles