Protonated sapphyrins. Highly effective phosphate receptors

Vladimír Král, Hiroyuki Furuta, Kevin Shreder, Vincent Lynch, Jonathan L. Sessler

Research output: Contribution to journalArticle

153 Citations (Scopus)

Abstract

The phosphate anion chelation properties of several sapphyrin derivatives, namely 3,12,13,22-tetraethyl-8,17-bis[bis(hydroxyethyl)amino)carbonylethyl]-2 ,7,18,23-tetramethylsapphyrin (1), 3,12,13,22-tetraethyl-2,7,18,23-tetramethyl-8,17-bis(hydroxypropyl)sap phyrin (2), and 3,8,12,13,17,22-hexaethyl-2,7,18,23-tetramethylsapphyrin (3) are reported. X-ray diffraction studies of the dihydroxylated and decaalkyl derivatives 2 and 3 reveal that the diprotonated forms of sapphyrin are capable of stabilizing 1:2 inner-sphere complexes with phosphate-derived monoanions, such as diphenyl phosphate and monobasic phenyl phosphate. Similar analyses reveal that the diprotonated form of dihydroxysapphyrin 2 is capable of forming a 1:1 chelate complex in the solid state with either mono- or dibasic phosphoric acid. Solution-phase studies, involving 1H and 31P NMR spectroscopy, confirm that these same sapphyrins are capable of binding phosphate anions in organic solution, a conclusion that is supported by qualitative fast atom bombardment mass spectrometric (FAB MS) and extractive partition studies. In the case of phenylphosphonic acid and sapphyrin 2, extraction studies were consistent with 2:1 and 1:1 phosphate-to-sapphyrin binding stochiometries at pH 1.68 and 5.6, respectively. Similar studies using NMR and visible spectroscopy carried out with the water-soluble tetrahydroxy sapphyrin derivative, 1, and 2 indicate that these species bind phosphate anion in both methanolic and aqueous solution. Calculated association constants are on the order of 104 M-1 in methanol and 102 M-1 in 10 mM aqueous bis-Tris, pH 6.1.

Original languageEnglish
Pages (from-to)1595-1607
Number of pages13
JournalJournal of the American Chemical Society
Volume118
Issue number7
DOIs
Publication statusPublished - Feb 21 1996
Externally publishedYes

Fingerprint

Phosphates
Anions
Negative ions
Derivatives
Magnetic Resonance Spectroscopy
Phosphoric acid
Chelation
sapphyrin
X-Ray Diffraction
Nuclear magnetic resonance spectroscopy
Methanol
Nuclear magnetic resonance
Association reactions
Spectroscopy
X ray diffraction
Atoms
Acids
Water

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Protonated sapphyrins. Highly effective phosphate receptors. / Král, Vladimír; Furuta, Hiroyuki; Shreder, Kevin; Lynch, Vincent; Sessler, Jonathan L.

In: Journal of the American Chemical Society, Vol. 118, No. 7, 21.02.1996, p. 1595-1607.

Research output: Contribution to journalArticle

Král, Vladimír ; Furuta, Hiroyuki ; Shreder, Kevin ; Lynch, Vincent ; Sessler, Jonathan L. / Protonated sapphyrins. Highly effective phosphate receptors. In: Journal of the American Chemical Society. 1996 ; Vol. 118, No. 7. pp. 1595-1607.
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AB - The phosphate anion chelation properties of several sapphyrin derivatives, namely 3,12,13,22-tetraethyl-8,17-bis[bis(hydroxyethyl)amino)carbonylethyl]-2 ,7,18,23-tetramethylsapphyrin (1), 3,12,13,22-tetraethyl-2,7,18,23-tetramethyl-8,17-bis(hydroxypropyl)sap phyrin (2), and 3,8,12,13,17,22-hexaethyl-2,7,18,23-tetramethylsapphyrin (3) are reported. X-ray diffraction studies of the dihydroxylated and decaalkyl derivatives 2 and 3 reveal that the diprotonated forms of sapphyrin are capable of stabilizing 1:2 inner-sphere complexes with phosphate-derived monoanions, such as diphenyl phosphate and monobasic phenyl phosphate. Similar analyses reveal that the diprotonated form of dihydroxysapphyrin 2 is capable of forming a 1:1 chelate complex in the solid state with either mono- or dibasic phosphoric acid. Solution-phase studies, involving 1H and 31P NMR spectroscopy, confirm that these same sapphyrins are capable of binding phosphate anions in organic solution, a conclusion that is supported by qualitative fast atom bombardment mass spectrometric (FAB MS) and extractive partition studies. In the case of phenylphosphonic acid and sapphyrin 2, extraction studies were consistent with 2:1 and 1:1 phosphate-to-sapphyrin binding stochiometries at pH 1.68 and 5.6, respectively. Similar studies using NMR and visible spectroscopy carried out with the water-soluble tetrahydroxy sapphyrin derivative, 1, and 2 indicate that these species bind phosphate anion in both methanolic and aqueous solution. Calculated association constants are on the order of 104 M-1 in methanol and 102 M-1 in 10 mM aqueous bis-Tris, pH 6.1.

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