Calix[3] amide-based Anion Receptors : High Affinity for Fluoride Ions and a Twisted Binding Model
Calix[3] amide-based Anion Receptors : High Affinity for Fluoride Ions and a Twisted Binding Model
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Calix[3] 酰胺基阴离子受体：对氟离子的高亲和力和扭曲的结合模型
DOI：
10.1080/10610278.2010.514909
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发表时间：
2011
影响因子：
3.3
通讯作者：
I.
中科院分区：
文献类型：
--
作者：
Katagiri;K.; Furuyama;T.; Masu;H.; Kato;T.; Matsumura;M.; Uchiyama;M.; Tanatani;A.; Tominaga;M.; Kagechika;H.; Yamaguchi;K.; Azumaya;I.
以胺为原料，分别与异氰酸酯和硫代异氰酸酯反应，合成了三苯基脲取代杯[3]酰胺（3a，3b）和三苯基硫脲取代杯[3]酰胺（4a，4 b）。单晶X-射线衍射分析表明，环状三聚体采用双链构象，所有的脲基团在同一侧。这些化合物对阴离子的结合亲和力用DMF-d 7，DMSO-d 6或CDCl 3中的1H NMR滴定法测量。每种受体都以1：1的化学计量比与卤素阴离子结合，完全通过氢键结合，阴离子选择性的顺序是F−> Cl− → Br−> I−。DFT计算表明，氟离子通过H···F相互作用锚定在3a的6个N-H氢原子的中心.
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 asynconformation with all of the urea groups on the same side. The binding affinities of these compounds towards anions were measured using1H NMR titrations in DMF-d7, DMSO-d6or 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 of3athrough H···F interactions.