Experimental and theoretical study on cation–π interaction of the univalent thallium cation with [2.2.2]paracyclophane

doi:10.1016/j.cplett.2015.10.074

Chemical Physics Letters

Volume 642, 1 December 2015, Pages 39-42

https://doi.org/10.1016/j.cplett.2015.10.074 Get rights and content

Highlights

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Electrospray ionization mass spectrometry was used for characterization of cation–π interaction.
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Cation Tl⁺ forms with [2.2.2]paracyclophane (C₂₄H₂₄) the complex [Tl(C₂₄H₂₄)]⁺.
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By employing DFT calculations, the most probable structure of the proven cation–π complex [Tl(C₂₄H₂₄)]⁺ was predicted.

Abstract

By using electrospray ionization mass spectrometry (ESI-MS), it was proven experimentally that the univalent thallium cation (Tl⁺) forms with [2.2.2]paracyclophane (C₂₄H₂₄) the cationic complex species [Tl(C₂₄H₂₄)]⁺. Further, employing quantum mechanical DFT calculations, the most probable structure of the [Tl(C₂₄H₂₄)]⁺ complex was derived. In the resulting complex with a symmetry very close to C₃, the ‘central’ cation Tl⁺ is bound by six bonding interactions to six carbon atoms from the three benzene rings of the parent [2.2.2]paracyclophane ligand via cation–π interaction.

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Acknowledgments

This work was supported by the Grant Agency of Faculty of Environmental Sciences, Czech University of Life Sciences, Prague, Project No.: 42900/1312/3114, ‘Environmental Aspects of Sustainable Development of Society’, and by the Czech Ministry of Education, Youth, and Sports (Project MSMT No.: 20/2015). The authors of this study thank Prof. Jaroslav Kvíčala from Prague for some theoretical calculations.

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Reaction of the thallium(I) cation with [2.2]paracyclophane: Experimental and theoretical study
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Electrospray ionization mass spectrometry was used to investigate the cation-π interaction of Tl⁺ cation with [2.2]paracyclophane. It was found that 1:1 cationic complex species is formed in the gas phase. Further, applying quantum mechanical calculations in the frame of the density functional theory, applying B3LYP functional with Def2TZVP basis set, the most probable structure of the proved [2.2]paracyclophane – Tl⁺ complex was derived. In the resulting complex, the cation Tl⁺ is bounded to six carbon atoms of one benzene ring of [2.2]paracyclophane ligand via cation-π interaction. The interaction energy, E(int), of this cation-π complex was calculated to be −133.59 kJ/mol, which is consistent with the formation of the considered Tl⁺ – [2.2]paracyclophane complex species.
Solvent extraction of europium(III) trifluoromethanesulfonate into nitrobenzene by using [2.2.2]paracyclophane – Experimental and theoretical study
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Citation Excerpt :
On the other hand, the binding energy of trivalent cation Eu3+ with [2.2.2]paracyclophane is much higher than that of univalent cations. We can add that the soft univalent cations Ag+ and Tl+ interact with [2.2.2]paracyclophane differently than both, alkali metal cations and Eu3+ [7,8]. While these cations are located in the center of the [2.2.2]paracyclophane cavity, Ag+ and Tl+ cations are located out off plane of ligand cavity, similarly as Sn(II) and Ge(II) [23].
The extraction constant corresponding to the equilibrium Eu³⁺(aq) + 3A^-(aq) + 1(nb) ⇌ 1 Eu³⁺(nb) + 3A^–(nb) occurring in the two-phase water–nitrobenzene system ( $A^{-} = {CF}_{3} {SO}_{3}^{-}$ ; 1 = [2.2.2]paracyclophane; aq = aqueous phase, nb = nitrobenzene phase) was determined as log K_ex(Eu³⁺,3A^–) = -5.7 ± 0.1. Further, the stability constant of the 1 Eu³⁺ complex in nitrobenzene saturated with water was calculated as log K_nb(1 Eu³⁺) = 7.4 ± 0.1. Finally, by using quantum chemical calculations, the most probable conformation of the cationic complex species 1 Eu³⁺ was derived. In the resulting complex, the “central” cation Eu³⁺, fully located in the cavity of the parent [2.2.2]paracyclophane ligand, is bound to all three benzene rings of [2.2.2]paracyclophane via cation-π interaction.
Interaction of Ag<sup>+</sup> with corannulene: Experimental and theoretical study
2021, Chemical Physics Letters
By using electrospray ionization mass spectrometry (ESI-MS), it was proven experimentally that the silver cation Ag⁺ forms with corannulene (C₂₀H₁₀) the cationic complex [Ag(C₂₀H₁₀)₂]⁺. Further, applying quantum chemical DFT calculations, the most probable structures of the [Ag(C₂₀H₁₀)₂]⁺ complex were derived. In the resulting complex the “central” cation Ag⁺, is located between two molecules of the corannulene ligand. Finally, the interaction energy, E(int), of the considered cation-π complex [Ag(C₂₀H₁₀)₂]⁺ was found to be −335.0 to −306.9 kJ/mol.
Interaction of the lithium cation with [2.2.2]paracyclophane: Experimental and theoretical study
2021, Journal of Molecular Structure
Citation Excerpt :
Recently, the first-principles model of Fermi resonance in the alkyl CH stretch region has been applied to 1,2-diphenylethane and [2.2.2]paracyclophane [12]. We must emphasize that the cation-π interactions of [2.2.2]paracyclophane (C24H24; see Fig. 1) with the “soft” cations Ag+ [9,10,13] and Tl+ [14] have been investigated. In our previous works, we dealt with the reaction of Na+, K+, Rb+ and Cs+and [2.2.2]paracyclophane in the gas phase [15–18].
By using electrospray ionization mass spectrometry (ESI-MS), it was proven experimentally that the univalent lithium cation (Li⁺) forms with [2.2.2]paracyclophane (C₂₄H₂₄) the cationic complex [Li(C₂₄H₂₄)]⁺. Further, applying quantum chemical DFT calculations, the most probable structure of the [Li(C₂₄H₂₄)]⁺ complex was derived. In the resulting complex with a symmetry very close to C₃, the “central” cation Li⁺, fully located in the cavity of the parent [2.2.2]paracyclophane ligand, is coordinated to all three benzene rings of [2.2.2]paracyclophane via cation-π interaction. Finally, the interaction energy, E(int), of the considered cation-π complex [Li(C₂₄H₂₄)]⁺ was found to be –324.7 kJ/mol, confirming the formation of this fascinating complex species as well.
Paracyclophane and [1 <inf>6</inf> ]paracyclophane: Facile syntheses, crystal structures and selective complexation with cesium cations in the gas phase
2019, Organic Chemistry Frontiers
Herein, we report the facile syntheses of [1₅]paracyclophane ([1₅]PCP, 1) and [1₆]paracyclophane ([1₆]PCP, 2) by hydrodeoxygenation of pillar[5]arene and pillar[6]arene via aryl fluorosulfate intermediates. The structures of [1₅]PCP and [1₆]PCP were confirmed by single crystal X-ray analysis for the first time. Moreover, their selective complexation with cesium cations in the gas phase was investigated by electrospray ionization mass spectrometry (ESI-MS) and confirmed by DFT calculations.
Experimental and theoretical study on cation-π interaction of the univalent silver cation with pyrene in the gas phase and in the solid state
2018, Inorganica Chimica Acta
Citation Excerpt :
Finally, the interaction energies, E(int), of the found conformers A, B, C, D, and E belonging to the complexes [Ag(C16H10)]+ and [Ag(C16H10)2]+, involving the 7-point corrections for the basis set superposition error (BSSE) [58,59], are reviewed in Table 1. At this point it should be stated that the interaction energies corresponding to the complexes [2.2.2]paracyclophane – Tl+ (i.e., [Tl(C24H24)]+) and [2.2.2]paracyclophane – Ag+ (i.e., [Ag(C24H24)]+) in the gas phase are −198.1 and −361.2 kJ/mol, respectively, as evaluated recently [60,61]. From comparison of the previous values with the data given in Table 1, it follows that in the gas phase, the stabilities of the conformers A, B, and C are roughly comparable with that of the [Tl(C24H24)]+ complex, whereas the interaction energies of the remaining conformers D and E are nearly comparable with that of [Ag(C24H24)]+.
By means of electrospray ionization mass spectrometry (ESI-MS), it was evidenced experimentally that the univalent silver cation (Ag⁺) reacts with the electroneutral pyrene ligand (C₁₆H₁₀) to form especially the cationic complexes [Ag(C₁₆H₁₀)]⁺ and [Ag(C₁₆H₁₀)₂]⁺. Moreover, applying quantum chemical calculations, five different conformations of these two Ag(I) complexes were derived. Finally, in the solid state, the polymeric complex structure [Ag(pyrene)_0.5(CF₃SO₃)]_n·[Ag(toluene)(CF₃SO₃)]_n, crystallizing in the monoclinic system with the centrosymmetric space group P2/c, was prepared and analyzed by X-ray crystallography.

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Experimental and theoretical study on cation–π interaction of the univalent thallium cation with [2.2.2]paracyclophane

Highlights

Abstract

Graphical abstract

Section snippets

Acknowledgments

Trends Pharm. Sci.

Coord. Chem. Rev.

Chem. Commun.

J. Am. Chem. Soc.

Chem. Eur. J.

J. Chem. Phys.

Science

Chem. Rev.

Chem. Rev.

Chem. Commun.

Inorg. Chem.

J. Phys. Chem. A

J. Phys. Chem. A

J. Phys. Chem. A

J. Am. Chem. Soc.