TY - JOUR
T1 - Calix[3]amide-based anion receptors
T2 - High affinity for fluoride ions and a twisted binding model
AU - Katagiri, Kosuke
AU - Furuyama, Taniyuki
AU - Masu, Hyuma
AU - Kato, Takako
AU - Matsumura, Mio
AU - Uchiyama, Masanobu
AU - Tanatani, Aya
AU - Tominaga, Masahide
AU - Kagechika, Hiroyuki
AU - Yamaguchi, Kentaro
AU - Azumaya, Isao
PY - 2011/1
Y1 - 2011/1
N2 - Tris-phenylurea-substituted calix[3]amides (3a, 3b) and tris-phenylthiourea-substituted calix[3]amides (4a, 4b) were synthesised by the reaction of amine with isocyanates and thioisocyanate, respectively. Single crystal X-ray analysis revealed that the cyclic trimers adopt a syn conformation with all of the urea groups on the same side. The binding affinities of these compounds towards anions were measured using 1H NMR titrations in DMF-d7, DMSO-d6 or CDCl3. Each receptor was observed to bind halogen anions in a 1:1 stoichiometry, exclusively through hydrogen bonding, and the anion selectivity was in the order F- > Cl- ≫ Br- > I- . DFT calculations revealed that the fluoride anion is anchored in the centre of the six N-H hydrogen atoms of 3a through H...F interactions.
AB - Tris-phenylurea-substituted calix[3]amides (3a, 3b) and tris-phenylthiourea-substituted calix[3]amides (4a, 4b) were synthesised by the reaction of amine with isocyanates and thioisocyanate, respectively. Single crystal X-ray analysis revealed that the cyclic trimers adopt a syn conformation with all of the urea groups on the same side. The binding affinities of these compounds towards anions were measured using 1H NMR titrations in DMF-d7, DMSO-d6 or CDCl3. Each receptor was observed to bind halogen anions in a 1:1 stoichiometry, exclusively through hydrogen bonding, and the anion selectivity was in the order F- > Cl- ≫ Br- > I- . DFT calculations revealed that the fluoride anion is anchored in the centre of the six N-H hydrogen atoms of 3a through H...F interactions.
KW - DFT calculations
KW - anion receptor
KW - calix[3]amide
UR - http://www.scopus.com/inward/record.url?scp=79952213074&partnerID=8YFLogxK
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U2 - 10.1080/10610278.2010.514909
DO - 10.1080/10610278.2010.514909
M3 - Article
AN - SCOPUS:79952213074
SN - 1061-0278
VL - 23
SP - 125
EP - 130
JO - Supramolecular Chemistry
JF - Supramolecular Chemistry
IS - 1-2
ER -