Towards the Design of Neutral Molecular Tweezers for Anion Recognition

Hermida-Ramón, José M.; Estévez, Carlos M.

doi:10.1002/chem.200601836

Cited by 33 publications

(26 citation statements)

References 33 publications

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“…Apart from the application of π-frameworks in building ion-selective receptors, 1,2,3,4 it has been demonstrated that these interactions are operative in defining the structures of biomolecules, 5,6,7,8,9,10,11,12 and have been used for catalysis. 13,14,15 Furthermore, the extent of ion-π interactions affects the capacity of energy-storage devices such as batteries and supercapacitors based on carbon nanostructures.…”

Section: Ion-π Interactionmentioning

confidence: 99%

Modulating Electron Sharing in Ion-π-Receptors via Substitution and External Electric Field: A Route toward Bond Strengthening

Novák

Foroutan‐Nejad

Marek

2016

J. Chem. Theory Comput.

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Substituted coronenes, a family of ion-π receptors whose ion-affinities can be explained exclusively neither via ion-quadrupole nor induction/polarization mechanisms, are studied. The best descriptors of ion-affinity among these species are those characterizing charge-transfer between ions and the π-systems, e.g. vertical ionization potential, electron affinity, and the relative energies of charge-transfer excited-states (CTESs). The variation of the electric multipole moments, polarizability, binding energy, and relative energy of CTESs in the presence of an external electric field (EEF) is evaluated. The results indicate that the EEF has a negligible effect on the polarizability and quadrupole moment of the systems. However, it significantly affects the binding energies, CTES energies, and the dipole moments of the receptors. Contrary to the changes in the dipole moment, the variation pattern of the binding energy is more consistent with the pattern observed for the CTES energy changes. Finally, by analyzing the exchange-correlation component of the binding energy we demonstrate that the increased binding energy, i.e. bond strengthening, originates from enhanced electron sharing and multicenter covalency between the ions and the π-systems as a result of the state-mixing between the ground-state and the CTESs. According to our findings, we hypothesize that the electron sharing and in extreme cases the multicenter covalency are the main driving forces for complexation of ions with extended π-receptors such as carbon nanostructures.

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Section: Ion-π Interactionmentioning

confidence: 99%

Modulating Electron Sharing in Ion-π-Receptors via Substitution and External Electric Field: A Route toward Bond Strengthening

Novák

Foroutan‐Nejad

Marek

2016

J. Chem. Theory Comput.

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“…Molecular tweezers can in principle be divided into three groups: semirigid, [6][7][8][9][10][11][12][13] conformationally labile, [2,[14][15][16][17][18][19][20] and conformationally controlled by hydrogen bonds or metal chelation. [21][22][23] The interaction that mediates the recognition process can, in addition to London dispersion forces, be based on hydrogen-bonding, [24] charge-transfer, [14] ion-p, [8,25] p-p, [1] electrostatic, [8] and coupled interactions. [26] Most common are molecular tweezers with high symmetry, but there are some chiral examples.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Self‐Aggregation of Enantiopure and Racemic Molecular Tweezers Based on the Bicyclo[3.3.1]nonane Framework

Wallentin¹,

Wixe²,

Wendt³

et al. 2010

Chemistry A European J

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A pair of molecular tweezers (syn-4) that consists of quinoline and pyrazine units fused to a bicyclic framework is presented. The tweezers were synthesised both as a racemic mixture (rac-4) and an enantiomerically pure form ((R,R,R,R)-4) starting from either racemic or enantiomerically pure bicyclo[3.3.1]nonane-2,6-dione (3). Homochiral dimers were observed in the solid state for rac-4. The self-association of both rac-4 and (R,R,R,R)-4 was studied in solution. A weak self-association constant in CDCl(3) was estimated by (1)H NMR spectroscopic dilution titration experiments in both cases, following several proton resonances. For this purpose, a general normalisation model for the accurate determination of association constants from multiple datasets was developed. In contrast to the solid state, no diastereomeric discrimination was observed for rac-4 in solution.

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“…[27][28][29][30][31][32] In fact, it has been shown that for example fluorination of benzene can lead to a favorable interaction with anions. [33][34][35][36][37] This effect can be used for designing molecular tweezers for anion recognition. 34 Also, the presence of heteroatoms in the skeleton of aromatic rings can modulate the characteristics of the interaction.…”

Section: Introductionmentioning

confidence: 99%

Computational study of the interaction of indole-like molecules with water and hydrogen sulfide

Cabaleiro‐Lago

Rodrı́guez-Otero

Peña‐Gallego

2011

The Journal of Chemical Physics

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The characteristics of the interaction between water and hydrogen sulfide with indole and a series of analogs obtained by substituting the NH group of indole by different heteroatoms have been studied by means of ab initio calculations. In all cases, minima were found corresponding to structures where water and hydrogen sulfide interact by means of X-H···π contacts. The interaction energies for all these π complexes are quite similar, spanning from -13.5 to -18.8 kJ/mol, and exhibiting the stability sequence NH > CH(2) ≈ PH > Se ≈ S > O, for both water and hydrogen sulfide. Though interaction energies are similar, hydrogen sulfide complexes are slightly favored over their water counterparts when interacting with the π cloud. σ-Type complexes were also considered for the systems studied, but only in the case of water complexes this kind of complexes is relevant. Only for complexes formed by water and indole, a significantly more stable σ-type complex was found with an interaction energy amounting to -23.6 kJ/mol. Oxygen and phosphorous derivatives also form σ-type complexes of similar stability as that observed for π ones. Despite the similar interaction energies exhibited by complexes with water and hydrogen sulfide, the nature of the interaction is very different. For π complexes with water the main contributions to the interaction energy are electrostatic and dispersive contributing with similar amounts, though slightly more from electrostatics. On the contrary, in hydrogen sulfide complexes dispersion is by far the main stabilizing contribution. For the σ-type complexes, the interaction is clearly dominated by the electrostatic contribution, especially in the indole-water complex.

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Towards the Design of Neutral Molecular Tweezers for Anion Recognition

Cited by 33 publications

References 33 publications

Modulating Electron Sharing in Ion-π-Receptors via Substitution and External Electric Field: A Route toward Bond Strengthening

Modulating Electron Sharing in Ion-π-Receptors via Substitution and External Electric Field: A Route toward Bond Strengthening

Synthesis and Self‐Aggregation of Enantiopure and Racemic Molecular Tweezers Based on the Bicyclo[3.3.1]nonane Framework

Computational study of the interaction of indole-like molecules with water and hydrogen sulfide

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