Anion binding with urea and thiourea derivatives

Bregović, Vesna Blažek; Basarić, Nikola; Mlinarić‐Majerski, Kata

doi:10.1016/j.ccr.2015.03.011

Cited by 277 publications

(97 citation statements)

References 386 publications

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“…We envisaged that these differences might impact upon both the hydrogen bond donor capability and Brønsted acidity of the analogous amides: the deltamides and croconamides (Figure ), and impact their anion binding abilities. While anion recognition by ureas and squaramides (including most of the compounds UR1 – 6 and SQ1 – 6 , Figure ) has been extensively investigated, there is only a single recent report of anion binding by the croconamides and the analogous N , N′ ‐disubstituted deltamides have not previously been reported. In order to compare the binding properties for monovalent anions of ureas, deltamides, squaramides, and croconamides we synthesized a systematic library of symmetrical croconamides CR1–CR6 and deltamides DT1–DT6 , bearing both alkyl and aryl substituents (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Deltamides and Croconamides: Expanding the Range of Dual H‐bond Donors for Selective Anion Recognition

Zwicker

Yuen

Smith

et al. 2017

Chemistry A European J

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Dual H-bond donors are widely used as recognition motifs in anion receptors. We report the synthesis of a library of dual H-bond receptors, incorporating the deltic and croconic acid derivatives, termed deltamides and croconamides, respectively, and a comparison of their anion binding affinities (for monovalent species) and Brønsted acidities to those of the well-established urea and squaramide dual H-bond donor motifs. For dual H-bonding cores with identical substituents, the trend in Brønsted acidity is croconamides>squaramides>deltamides>ureas, with the croconamides found to be 10-15 pK units more acidic than the corresponding ureas. In contrast to the trends displayed by ureas, deltamides and squaramides, N,N'-dialkyl croconamides displayed higher binding affinity to chloride than the N,N'-diaryl derivatives, which was attributed to partial deprotonation of the N,N'-diaryl derivatives at neutral pH. A number of differences in anion binding selectivity were observed upon comparison of the dual H-bond cores. Whereas the squaramides display similar affinity for both chloride and acetate ions, the ureas have significantly higher affinity for acetate than chloride ions and the deltamides display higher affinity for dihydrogenphosphate ions than other oxoanions or halides. These inherent differences in binding affinity could be exploited in the design of anion receptors with improved ability to discriminate between monovalent anions.

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Section: Introductionmentioning

confidence: 99%

Deltamides and Croconamides: Expanding the Range of Dual H‐bond Donors for Selective Anion Recognition

Zwicker

Yuen

Smith

et al. 2017

Chemistry A European J

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“…The nature and use of the macrocycles are decided by their shape, synthesis, solubility in organic solvents and aqueous media, their functionalization and their host-guest binding ability [4]. Among the macrocyclic molecules, the selective molecular recognition and self-assembly properties of several classical supramolecular macrocycles, including that of, crown ethers [5], cyclophanes [6], cyclodextrins (CDs) [7,8], cucurbit[n] urils (CB[n]) [9,10], calix[n]arenes [11,12], and Pillar[n] arenes [13] were well documented. Furthermore, most of these macrocycles are neutral molecules and are capable of binding charged guest molecules.…”

Section: Introductionmentioning

confidence: 99%

Structure, electronic, inclusion complex formation behavior and spectral properties of pillarplex

Venkataramanan

Suvitha

2017

J Incl Phenom Macrocycl Chem

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systems. The low binding energy, and the physical adsorption of guest molecule and HOMO-LUMO spatial diagram indicates, that the Au and Ag-Pillarplex can be used as reversible host for linear alkanes Complexation of guest engenders frequency shift in the vibrational spectra. Calculated 1 H NMR reveal that guest protons which are closer to the metal sites experience larger shielding possibly due to C-H→LP* metal interaction. The 15 N signal observed for the DAO is nearly identical to that observed for the DAO@ metal-Pillarplex. NBO and AIM analysis indicate that metal centers in host, play a major role in stabilizing the guest inside the cavity than the amino group on the guest molecule.Abstract Electronic structure, vibrational and NMR spectra of metal-Pillarplex (metal = Cu, Ag and Au) and its inclusion complex with 1,8-diaminooctane (DAO) are investigated by using density functional theory. The coordinated metal atoms tune the cavity size and the height of metal-Pillarplex and form a rigid cavity thereby reducing their structural deformation. Cu-Pillarplex undergoes a large deformation both on the host and guest molecule. The calculated Gibbs free energy for the formation of inclusion complex were negative indicating their facile formation at the room temperature. Computed binding energies with various functionals and energy decomposition analysis, shows that dispersion correction is essential in these Electronic supplementary material The online version of this article (

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“…Binding of these anions to 22 urea‐, carbazole‐ and indolocarbazole‐based receptors (see Scheme ) was measured in [D 6 ]DMSO with 0.5 % of water. Polydentate systems in which several NH centres can form hydrogen bonds with carboxylate centre are among the most suitable building blocks for selecting receptors for carboxylate anions , . For this reason, tetra‐ to hexadentate receptors dominate the selection.…”

Section: Introductionmentioning

confidence: 99%

Exploring Selectivity of 22 Acyclic Urea‐, Carbazole‐ and Indolocarbazole‐Based Receptors towards 11 Monocarboxylates

et al. 2017

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Carboxylates are attractive target analytes in supramolecular analytical chemistry. 22 acyclic synthetic receptors with different numbers and geometric arrangements of hydrogen‐bond donors (HBD) and hydrophobic moieties have been applied to experimentally study selective binding of 11 carboxylate anions of widely differing basicity, hydrophobicity and steric demand, which resulted in 242 accurately determined binding constants. It was found that besides the basicity of the anions, structural and steric factors of anions and receptors influence the binding. Several interesting cases are pinpointed and analysed. The ability of selected receptors to discriminate between anions according to structural features (hydrophilicity, substitution at α‐carbon, etc.) is demonstrated. The present results give insight into carboxylate anion binding and make an important step towards systematic development of receptors with useful selectivity patterns and thereby to the practical use of receptor series in sensor arrays for carboxylate fingerprinting in mixtures.

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Anion binding with urea and thiourea derivatives

Cited by 277 publications

References 386 publications

Deltamides and Croconamides: Expanding the Range of Dual H‐bond Donors for Selective Anion Recognition

Deltamides and Croconamides: Expanding the Range of Dual H‐bond Donors for Selective Anion Recognition

Structure, electronic, inclusion complex formation behavior and spectral properties of pillarplex

Exploring Selectivity of 22 Acyclic Urea‐, Carbazole‐ and Indolocarbazole‐Based Receptors towards 11 Monocarboxylates

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