Selective recognition of dihydrogen phosphate by receptors bearing pyridyl moieties as hydrogen bond acceptors

Anions are important hydrogen bond acceptors in a range of biological, chemical, environmental and medical molecular recognition processes.<sup> </sup>These interactions have been exploited for the design and synthesis of ditopic resorcinarenes as the hydrogen bond strength can be tuned through the modification of the substituent at the 2-position. However, many potentially useful compounds, especially those incorporating electron-withdrawing functionalities, have not been prepared due to the challenge of their synthesis: their incorporation slows resorcinarene formation that is accessed by electrophic aromatic substitution. As part of our broader campaign to employ resorcinarenes as selective recognition elements, we need access to these specialized materials, and in this article we report a straightforward synthetic pathway for obtaining a 2-(carboxymethyl)-resorcinarene, and resorcinarene esters in general. We discuss the unusual conformation it adopts, and propose that this arises from the electron-withdrawing nature of the ester substituents that renders them better hydrogen bond acceptors than the phenols, ensuring that each of those acts as a donor only. DFT calculations show that this conformation arises as a consequence of the unusual configurational isomerism of this compound and interruption of the archetypal hydrogen bonding by the ester functionality.

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Synthesis of Tris-pillar[5]arene and Its Association with Phenothiazine Dye: Colorimetric Recognition of Anions

Molecules ◽

10.3390/molecules24091807 ◽

2019 ◽

Vol 24 (9) ◽

pp. 1807 ◽

Cited By ~ 5

Author(s):

Alena Khadieva ◽

Vladimir Gorbachuk ◽

Dmitriy Shurpik ◽

Ivan Stoikov

Keyword(s):

Hydrogen Bond ◽

1H Nmr Spectroscopy ◽

Color Change ◽

Amide Group ◽

Anion Binding ◽

Dihydrogen Phosphate ◽

Imino Group ◽

Colorimetric Probe ◽

Arene Complex ◽

Phosphate Anions

A multicyclophane with a core based on tris(2-aminoethyl)amine (TREN) linked by amide spacers to three fragments of pillar[5]arene was synthesized. The choice of the tris-amide core allowed the multicyclophane to bind to anion guests. The presence of three terminal pillar[5]arene units provides the possibility of effectively binding the colorimetric probe N-phenyl-3-(phenylimino)-3H-phenothiazin-7-amine (PhTz). It was established that the multicyclophane complexed PhTz in chloroform with a 1:1 stoichiometry (lgKa = 5.2 ± 0.1), absorbing at 650 nm. The proposed structure of the complex was confirmed by 1H-NMR spectroscopy: the amide group linking the pillar[5]arene to the TREN core forms a hydrogen bond with the PhTz imino-group while the pillararenes surround PhTz. It was established that the PhTz:tris-pillar[5]arene complex could be used as a colorimetric probe for fluoride, acetate, and dihydrogen phosphate anions due to the anion binding with proton donating amide groups which displaced the PhTz probe. Dye displacement resulted in a color change from blue to pink, lowering the absorption band at 650 nm and increasing that at 533 nm.

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Rational design of a functionalized oxacalix[2]arene[2]triazine host for selective recognition of H2PO4− by cooperative anion–π and hydrogen bond interactions

Tetrahedron Letters ◽

10.1016/j.tetlet.2012.09.005 ◽

2012 ◽

Vol 53 (46) ◽

pp. 6226-6229 ◽

Cited By ~ 15

Author(s):

Sen Li ◽

De-Xian Wang ◽

Mei-Xiang Wang

Keyword(s):

Hydrogen Bond ◽

Rational Design ◽

Selective Recognition ◽

Hydrogen Bond Interactions

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C 3v-symmetric anion receptors with guanidine recognition motifs for ratiometric sensing of fluoride

RSC Advances ◽

10.1039/c5ra26039f ◽

2016 ◽

Vol 6 (10) ◽

pp. 7872-7878 ◽

Cited By ~ 7

Author(s):

Won Kim ◽

Suban K. Sahoo ◽

Gi-Dong Kim ◽

Heung-Jin Choi

Keyword(s):

Hydrogen Bond ◽

Selective Recognition ◽

Anion Receptors ◽

Ratiometric Sensing ◽

Recognition Motifs

Two new tripodal receptors 3 and 4 derived from a trindane framework having guanidine groups acting as hydrogen bond acceptors are synthesized and characterized for the selective recognition of anions.

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Revision of Ferroelastic Structures of n-Heptyl- and n-Octylammonium Dihydrogen Phosphate Crystals

Acta Crystallographica Section B Structural Science ◽

10.1107/s0108768196012426 ◽

1997 ◽

Vol 53 (2) ◽

pp. 272-279 ◽

Cited By ~ 4

Author(s):

J. Fábry ◽

V. Petrícek ◽

I. Císarová ◽

J. Kroupa

Keyword(s):

Hydrogen Bond ◽

Hydrogen Bonds ◽

Structure Determination ◽

Symmetry Operation ◽

Double Layers ◽

Dihydrogen Phosphate ◽

Hydrogen Bond Acceptor ◽

Space Group ◽

Unit Cells ◽

Pass Through

This study deals with the structure determination of C7H15NH3 +.H2PO4 − (C7ADP) and C8H17NH3 +.H2PO4 − (C8ADP). The samples used in this study were not subjected to a phase transition after they had been crystallized. Unlike a previous structure determination, weak reflections, now with indices h = 2n + 1, were included. This means that both structures are described in unit cells with the lattice parameters a twice as long as given previously. Both structures are quite similar; two double layers of dihydrogen phosphates, which are interconnected by hydrogen bonds (2.52–2.62 Å), pass through each unit cell. Alkylammonium groups interact with these dihydrogen phosphates via longer hydrogen bonds (>2.75 Å), while the rest of the aliphatic chains interact via van der Waals contacts. All H atoms were localized and no disorder of the H atoms was detected. Both structures described in the space group P121/n1 exhibit a reproducible ferroelastic switching. The hypothetical prototypic phase is orthorhombic with the space group number 60 P2/b21/n21/a. All atoms except two hydrogen species exist in pairs linked by the lost symmetry operations derived from the prototypic space group and are brought close to each other – up to 0.25 Å – under the action of them. Each of these two different H atoms is involved in an asymmetric hydrogen bond between an oxygen pair. Under the action of a lost symmetry operation each of these H atoms is displaced from one oxygen towards the other. Therefore, it is assumed that during the ferroelastic switching the jumps of these two hydrogen species take place between the pertinent hydrogen-bond acceptor and donor O atoms. Hence, these O atoms reverse their role as hydrogen-bond donors and acceptors during the ferroelastic switching.

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