Acid/Base Controlled Size Modulation of Capsular Phosphates, Hydroxide Encapsulation, Quantitative and Clean Extraction of Sulfate with Carbonate Capsules of a Tripodal Urea Receptor

dc.contributor.utaustinauthorRavikumar, I.en_US
dc.creatorAkhuli, Bidyuten_US
dc.creatorRavikumar, I.en_US
dc.creatorGhosh, Pradyuten_US
dc.description.abstractA simple tris-(2-aminoethyl) amine based pentafluorophenyl substituted tripodal urea receptor L has been extensively studied as a versatile receptor for various anions. Combined H-1-NMR, Isothermal Titration Calorimetry (ITC) and single crystal X-ray diffraction studies reveal that mononegative anions like F-, OH- and H2PO4- are encapsulated into the pseudocapsular dimeric assemblies of L with 1 : 1 stoichiometry whereas dinegative anions like CO32-, SO42- and HPO42- form tight capsular dimeric assemblies of L with 1 : 2 stoichiometries. Single crystal X-ray diffraction study clearly depicts that the size of the dimer of H2PO4- encapsulated pseudocapsule is 13.8 angstrom whereas the size of the tight HPO42- encapsulated capsular assembly is only 9.9 angstrom. The charge dependent anion encapsulated capsular size modulation of phosphates has been demonstrated by simple acid/base treatment via solution state P-31-NMR and single crystal X-ray diffraction studies. L is also capable of encapsulating hydroxide in its C-3v-symmetric cavity that is achieved upon treating a DMSO solution of L with tetrabutylammonium (TBA) cyanide and characterized by single crystal X-ray diffraction study. To the best of our knowledge this is the first report on the encapsulation of hydroxide in a neutral synthetic receptor. The excellent property of L to quantitatively capture aerial CO2 in the form of CO32- capsules [L-2(CO3)][N(n-Bu)(4)](2) in basic DMSO solution has been utilized to study the liquid-liquid extraction of SO42- from water via anion exchange. Almost quantitative and clean extraction of SO42- from water (99% from extracted pure mass and > 95% shown gravimetrically) has been unambiguously demonstrated by NMR, FT-IR, EDX, XRD and PXRD studies. Selective SO42- extraction is also demonstrated even in the presence of H2PO4- and NO3-. On the other hand the mixtures of L and TBACl (to solubilize L in CHCl3) results impure sulfate extraction even when 1 : 1 L/TBACl is used. Similar impure SO42- extraction is also observed when organic layers containing [L(Cl)][N(n-Bu)(4)] are used as the extractant, obtained upon precipitating SO42- from the extracted mass, [L-2(SO4)][N(n-Bu)(4)](2) in the carbonate capsules method using aqueous BaCl2 solution.en_US
dc.description.sponsorshipDepartment of Science and Technologyen_US
dc.description.sponsorshipCSIR, Indiaen_US
dc.identifier.citationAkhuli, Bidyut, I. Ravikumar, and Pradyut Ghosh. "Acid/base controlled size modulation of capsular phosphates, hydroxide encapsulation, quantitative and clean extraction of sulfate with carbonate capsules of a tripodal urea receptor." Chemical Science 3, no. 5 (Jan., 2012): 1522-1530.en_US
dc.relation.ispartofserialChemical Scienceen_US
dc.rightsAdministrative deposit of works to Texas ScholarWorks: This works author(s) is or was a University faculty member, student or staff member; this article is already available through open access or the publisher allows a PDF version of the article to be freely posted online. The library makes the deposit as a matter of fair use (for scholarly, educational, and research purposes), and to preserve the work and further secure public access to the works of the University.en_US
dc.subject3-dialkylaminomethylsalicylaldimine unitsen_US
dc.subjectchemistry, multidisciplinaryen_US
dc.titleAcid/Base Controlled Size Modulation of Capsular Phosphates, Hydroxide Encapsulation, Quantitative and Clean Extraction of Sulfate with Carbonate Capsules of a Tripodal Urea Receptoren_US

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