Tris(3-aminopropyl)amine-based tripodal urea and thiourea receptors, tris([(4-cyanophenyl)amino]propyl)urea (L1) and tris([(4-cyanophenyl)amino]propyl)thiourea (L2), have been synthesized and their anion binding properties have been investigated for halides and oxoanions. As investigated by 1H NMR titrations, each receptor binds an anion with a 1:1 stoichiometry via hydrogen-bonding interactions (NH⋯anion), showing the binding trend in the order of F− > H2PO4− > HCO3− > HSO4− > CH3COO− > SO42− > Cl− > Br− > I in DMSO-d6. The interactions of the receptors were further studied by 2D NOESY, showing the loss of NOESY contacts of two NH resonances for the complexes of F−, H2PO4−, HCO3−, HSO4− or CH3COO− due to the strong NH⋯anion interactions. The observed higher binding affinity for HSO4− than SO42− is attributed to the proton transfer from HSO4− to the central nitrogen of L1 or L2 which was also supported by the DFT calculations, leading to the secondary acid-base interactions. The thiourea receptor L2 has a general trend to show a higher affinity for an anion as compared to the urea receptor L1 for the corresponding anion in DMSO-d6. In addition, the compound L2 has been exploited for its extraction properties for fluoride in water using a liquid-liquid extraction technique, and the results indicate that the receptor effectively extracts fluoride from water showing ca. 99% efficiency (based on L2).
A new hexaurea receptor has been synthesized, which absorbs atmospheric CO2 to produce an air-stable solid carbonate complex under normal conditions. Structural analysis of the carbonate complex with this receptor suggests that the carbonate is fully encapsulated within its highly organized intramolecular cavity via twelve strong NH···O bonds in the range of 2.703(3) – 2.989(3) Å from six urea units, with each anionic oxygen coordinated via four NH···O bonds with two urea groups.
The
anion-binding properties of two tripodal-based hexaureas appended
with the m-nitrophenyl (1) and pentafluorophenyl
(2) groups have been studied both experimentally and
theoretically, showing strong affinities for sulfate over other inorganic
oxoanions such as hydrogen sulfate, dihydrogen phosphate, bicarbonate,
nitrate, and perchlorate. The structural analysis of the sulfate complex
with 1 reveals that the receptor organizes all urea-binding
sites toward the cavity at precise orientations around a tetrahedral
sulfate anion to form an ideal C3-symmetric
sulfate complex that is stabilized by 12 hydrogen-bonding interactions.
The receptor and the encapsulated sulfate are located on the threefold
axis passing through the bridgehead nitrogen of 1 and
the sulfur atom of the anionic guest. The high-level density functional
theory calculations support the crystallographic results, demonstrating
that the C3-symmetric conformation of
the sulfate complex is achieved due to the complementary NH···O
between the receptor and sulfate.
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