Binding and removal of sulfate, phosphate, arsenate, tetrachloromercurate, and chromate in aqueous solution by means of an activated carbon functionalized with a pyrimidine-based anion receptor (HL). Crystal structures of [H3L(HgCl4)]·H2O and [H3L(HgBr4)]·H2O showing anion-π interactions.
Binding of anions of great environmental concern such as SO(4)(2-), PO(4)(3-), AsO(4)(3-), HgCl(4)(2-), and CrO(4)(2-) by the protonated forms of a tren-like (tren = tris(2-aminoethyl)amine) ligand (HL) functionalized with a pyrimidine residue was studied by means of potentiometric measurements and isothermal titration calorimetry (ITC) affording log K, ΔH°, and TΔS° values for the formation of the relevant complexes. The complexes show high to very high stability due to the particular topology and electronic properties of the ligand which is able to use two separated coordination environments to host the anions, the protonated tren site where electrostatic and hydrogen bond interactions are operating, and the pyrimidine ring which may act via anion-π interaction. A contribution of -8.9 ± 0.4 kJ/mol for pyrimidine-anion interaction in water was derived for SO(4)(2-) binding. The crystal structures of [H(3)L(HgCl(4))]·H(2)O (1), [H(3)L(HgBr(4))]·H(2)O (2), and that previously reported for [H(3)L(CdI(4))], clearly show these binding features in the solid state. A hybrid AC-HL material obtained by adsorption of HL on commercial activated carbon (AC) was used to study the removal of these anions from water. AC-HL shows enhanced adsorption capacity toward all the anions studied with respect to AC. This behavior is ascribed to the stronger interaction of anions with the HL function of AC-HL than with the Cπ-H(3)O(+) sites of the unfunctionalized AC.
Arranz
Paloma
P
Departament of Inorganic and Organic Chemistry, University of Jaén, 23071, Jaén, Spain.
Bianchi
Antonio
A
Cuesta
Rafael
R
Giorgi
Claudia
C
Godino
M Luz
ML
Gutiérrez
M D
MD
López
Rafael
R
Santiago
Antonio
A
D000327:Adsorption; D001149:Arsenates / Q000737:chemistry / Q000302:isolation & purification; D002244:Carbon / Q000737:chemistry*; D002840:Chromates / Q000737:chemistry / Q000302:isolation & purification; D018360:Crystallography, X-Ray; D005029:Ethylenediamines / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D009941:Organomercury Compounds / Q000737:chemistry*; D010710:Phosphates / Q000737:chemistry / Q000302:isolation & purification; D011522:Protons; D011743:Pyrimidines / Q000737:chemistry*; D012996:Solutions; D013431:Sulfates / Q000737:chemistry / Q000302:isolation & purification; D014867:Water / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000737:chemistry* / Q000302:isolation & purification*
D001149:Arsenates; D002840:Chromates; D005029:Ethylenediamines; D008024:Ligands; D009941:Organomercury Compounds; D010710:Phosphates; D011522:Protons; D011743:Pyrimidines; D012996:Solutions; D013431:Sulfates; D014874:Water Pollutants, Chemical; D014867:Water; C099539:tris(2-aminoethyl)amine; D002244:Carbon; C030986:pyrimidine