Title: Phenanthroline-strapped calix[4]pyrroles: anion receptors displaying affinity reversal as a function of solvent polarity

Journal Article · · Organic Chemistry Frontiers (Online)
DOI: https://doi.org/10.1039/c9qo01377f · OSTI ID:1800009
 [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [2]
  1. Gyeongsang National Univ., Jinju (Korea, Republic of). Dept. of Chemistry. Research Inst. of Natural Science; OSTI
  2. Gyeongsang National Univ., Jinju (Korea, Republic of). Dept. of Chemistry. Research Inst. of Natural Science
  3. Hallym Univ., Chuncheon (Korea, Republic of). Dept. of Chemistry. Inst. of Applied Chemistry
  4. Hunan Univ., Changsha (China). State Key Lab. of Chemo/Biosensing and Chemometrics. College of Chemistry and Chemical Engineering
  5. Univ. of Texas, Austin, TX (United States). Dept. of Chemistry
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Calix[4]pyrroles 1 and 2, diametrically strapped with a phenanthroline via ester and amide linkages, respectively, have been synthesized as anion receptors. It was revealed by 1H NMR spectroscopic analysis that receptors 1 and 2 possessing both hydrogen bonding donors and acceptors were able to bind the bicarbonate anion (as its tetraethylammonium (TEA+) or sodium salt) in CDCl3, as well as in 15% aqueous DMSO with high affinity and selectivity over other anions. The amide-based receptor 2 contains additional potential hydrogen bonding donors relative to its ester-based congener 1. Nevertheless, in CDCl3 receptor 1 was found to display a higher affinity for all test anions than receptor 2. In contrast, in 15% aqueous DMSO solution the affinities of receptor 2 for anions, in particular chloride, bicarbonate, and dihydrogen phosphate, were enhanced, whereas those of receptor 1 were reduced dramatically with no appreciable interaction being seen in the case of most test anions considered in this study. These reversals in selectivity and affinities underscore the importance of solvent in regulating the recognition features of seemingly similiar anion binding agents.

Research Organization:
Univ. of Texas, Austin, TX (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-01ER15186
OSTI ID:
1800009
Journal Information:
Organic Chemistry Frontiers (Online), Journal Name: Organic Chemistry Frontiers (Online) Journal Issue: 3 Vol. 7; ISSN 2052-4129
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY