Screening Solvent Effects in Anion Recognition

Cockroft, Scott L.

doi:10.1016/j.chempr.2017.08.008

Cited by 14 publications

(16 citation statements)

References 11 publications

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“…Alternatively, the cation might be located on top of the anion resulting in an ion‐paired complex with close‐contact binding mode . In more polar organic solvents, like acetone or acetonitrile, the influence of the cation in the binding process is reduced owing to the partial dissociation of the salt ion‐pair and the resulting ion‐paired complexes.…”

Section: Introductionmentioning

confidence: 99%

“…Alternatively,t he cation might be located on top of the anion resulting in an ion-paired complex with close-contact binding mode. [10] In more polar organic solvents, like acetone or acetonitrile, [15,16] the influence of the cation in the binding process is reduced owing to the partial dissociation of the salt ion-pair and the resulting ion-paired complexes. The introduction of electron-withdrawing and electron-donating groups on the para and meta positions of the meso-aryl substituents (upper rim) of "two-wall" a,a-calix [4]pyrroles modulates their binding affinity towards anions.…”

Section: Introductionmentioning

confidence: 99%

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Influence of the Attachment of a Gold(I) Phosphine Moiety at the Upper Rim of a Calix[4]pyrrole on the Binding of Tetraalkylammonium Chloride Salts

Sun

Aragay

Pinto

et al. 2020

Chemistry A European J

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We report the synthesis of an unprecedented mono‐gold(I) phosphine complex based on a “two‐wall” aryl‐ethynyl extended calix[4]pyrrole. We describe and compare the binding properties of the parent 10α,20α‐bis‐aryl‐ethynyl calix[4]pyrrole ligand and the prepared organometallic compound as receptors for tetraalkylammonium chloride salts in dichloromethane and acetone. We describe the results of 1H NMR, UV–Vis titrations and isothermal titration calorimetry (ITC) experiments in dichloromethane and acetone, aiming to thermodynamically characterize the formed complexes. The obtained results indicate a noticeable decrease in the binding affinity of the chloride for the mono‐gold(I) receptor 1 compared to the parent ligand 2. The increase in the negative value of the electrostatic surface potential at the center of the aromatic ring of the gold(I) meso‐aryl‐ethynyl substituent serves to explain the observed results and the presence in solution of the chloride complex of 1 as a mixture of two conformers.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Influence of the Attachment of a Gold(I) Phosphine Moiety at the Upper Rim of a Calix[4]pyrrole on the Binding of Tetraalkylammonium Chloride Salts

Sun

Aragay

Pinto

et al. 2020

Chemistry A European J

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show abstract

“…Thee nhancement of interactions in less polar solvents were reported, for example, in an anion recognition system. [59,60] Solvents such as [D 8 ]THF showed coordination to the metal ion. Theb ias towards the heterocomplex was preserved in all the investigated solvents (see SI Chapter 7.5).…”

Section: Methodsmentioning

confidence: 99%

Noncovalent CH–π and π–π Interactions in Phosphoramidite Palladium(II) Complexes with Strong Conformational Preference

2021

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The weak noncovalent interactions and flexibility of ligands play ak ey role in enantioselective metal-catalyzed reactions.I nt ransition metal complexes and their catalytic applications,the experimental assessment and the design of key interactions is as difficult as the prediction of the enantioselectivities,e specially for flexible,p rivileged ligands such as chiral phosphoramidites.T herefore,t he interligand interactions in cis-Pd II L 2 Cl 2 phosphoramidite complexes were investigated by NMR spectroscopyand computations.W ewere able to induce as trong conformational preference by breaking the symmetry of the C 2 -symmetric side chain of one of the ligands, and shift the equilibrium between hetero-and homocomplexes towards heterocomplexes because of interligand interactions in the cis-complexes.T he modulation of aryl substituents was exploited, along with the solvent effect. The combined CH-p and p-p interactions reveal design patterns for binding and folding of chiral ligands and catalysts.

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“…[15,16,[36][37][38][39][40] There is a plethora of papers that make use of computational tools for both these purposes, highlighting future challenges for the study of host-guest chemistry. [41][42][43][44] The anion-π interaction has been a controversial topic among chemists, [45][46][47][48][49] due to the counterintuitive idea that negatively charged species could interact attractively with aromatic π-clouds. Ultimately, numerous anion-π based studies have led to the development of novel supramolecular systems [26,27,50] as well as advances in catalysis, [51][52][53][54] medicinal chemistry, and biochemistry, [55][56][57] all of which support the continued drive to gain insight into this specific NCI.…”

Section: Introductionmentioning

confidence: 99%

“…Calculations performed on systems containing non‐covalent interactions can either lead to empirical validation, or instead, aid the rationalization of experimental results to further encourage the design and synthetic exploration of novel host species . There is a plethora of papers that make use of computational tools for both these purposes, highlighting future challenges for the study of host‐guest chemistry …”

Section: Introductionmentioning

confidence: 99%

In Silico Design of Cylindrophanes: The Role of Functional Groups in a Fluoride Selective Host

et al. 2020

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Molecular recognition is the key driver in the formation of supramolecular complexes, enabling the selective encapsulation of specific guests. Here, we explore the delicate balance between different energetic terms in the formation of an efficient host for fluoride anions based on a cylindrophane structure, which can be achieved by the incorporation of ligand sites into a cyanuric acid based cyclophane framework, resulting a close proximity between the ammonium hydrogens and the anion. This study describes the character and contribution of different energetic and repulsive terms that favor the efficient inclusion of fluoride. Our findings are useful for further rational design and synthesis of efficient and highly selective fluoride hosts, which have been generally less well described than complexing agents for other halides.

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Screening Solvent Effects in Anion Recognition

Cited by 14 publications

References 11 publications

Influence of the Attachment of a Gold(I) Phosphine Moiety at the Upper Rim of a Calix[4]pyrrole on the Binding of Tetraalkylammonium Chloride Salts

Influence of the Attachment of a Gold(I) Phosphine Moiety at the Upper Rim of a Calix[4]pyrrole on the Binding of Tetraalkylammonium Chloride Salts

Noncovalent CH–π and π–π Interactions in Phosphoramidite Palladium(II) Complexes with Strong Conformational Preference

In Silico Design of Cylindrophanes: The Role of Functional Groups in a Fluoride Selective Host

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