Cation–π interaction of Ag+ with [6]helicene: An experimental and theoretical study

Makrlík, Emanuel; Dytrtová, Jana Jaklová; Vaňura, Petr; Sýkora, Ján; Cı́rkva, Vladimı́r; Storch, Jan

doi:10.1016/j.cplett.2015.04.029

Cited by 12 publications

(9 citation statements)

References 37 publications

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“…The geometric structures of the PAHs, hydrated HMs and PAH-HM complexes were optimized using density functional theory (DFT) with the B3PW91 function in the Gaussian 09 software package . The geometry optimization and single-point energies were calculated by the 6-311++G(d,p) basis set using the high-grid option int(grid = ultrafine). , The integral equation formalism model (IEEPCM) was applied in the present study to investigate the effect of solvent (water) on the chemical stabilities of hydrated metals, PAHs, and PAH-HM complexes. In an aqueous solution, four-, five- and six-coordinated conformers are possible for Cu 2+ (d 9 cation) and Zn 2+ (d 10 cation) hydrates .…”

Section: Materials and Methodsmentioning

confidence: 99%

Cation−π Interactions with Coexisting Heavy Metals Enhanced the Uptake and Accumulation of Polycyclic Aromatic Hydrocarbons in Spinach

Chen

Xia

Chu

et al. 2020

Environ. Sci. Technol.

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Few studies have considered the effect of cooccurring heavy metals on plant accumulation of hydrophobic organic compounds (HOCs), and less is known about the role of intermolecular interactions. This study investigated the molecular mechanisms of Cu/Zn effects on hydroponic uptake of four deuterated polycyclic aromatic hydrocarbons (PAHs-d 10 ) by spinach (Spinacia oleracea L.). Both solubility enhancement experiment and quantum mechanical calculations demonstrated the existence of [PAH-Cu(H 2 O) 0−4 ] 2+ and [2•PAH-Cu-(H 2 O) 0−2 ] 2+ via cation−π interactions when Cu 2+ concentration was ≤100 μmol/L. Notably, PAH-d 10 concentrations in both roots and shoots increased significantly with Cu 2+ concentration. This was because the formation of phytoavailable PAH-Cu 2+ complexes decreased PAH-d 10 hydrophobicity and consequently decreased their sorption onto dissolved organic carbon (DOC, i.e., root exudates), thereby increasing phytoavailable concentrations and uptake of PAHs-d 10 . X-ray absorption near-edge structure analysis showed that PAH-Cu 2+ complexes could enter defective spinach roots via apoplastic pathway. However, Zn 2+ and PAHs-d 10 cannot form the cation−π interactions because of the high desolvation penalty of Zn 2+ . Actually, Zn 2+ decreased the spinach uptake of PAHs-d 10 due to the increase of DOC induced by Zn. This work provides molecular insights into how metals could selectively affect the plant uptake of HOCs and highlights the importance of considering the HOC phytoavailability with coexisting metals.

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Section: Materials and Methodsmentioning

confidence: 99%

Cation−π Interactions with Coexisting Heavy Metals Enhanced the Uptake and Accumulation of Polycyclic Aromatic Hydrocarbons in Spinach

Chen

Xia

Chu

et al. 2020

Environ. Sci. Technol.

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“…The present study investigates the Ag + complexes of 5,7,12, 14-tetraphenyl-substituted 6,13-diazapentacene and its reduced 6,13-dihydro counterpart. 12,13 The motivation for this work originates from the importance of the silver(I) cation for the ion formation of unsaturated hydrocarbons [14][15][16][17][18][19][20][21][22] and, in particular, polycyclic aromatic hydrocarbons (PAHs) [23][24][25][26][27] which enables the application of electrospray ionization mass spectrometry (ESI-MS) for the analysis of these compounds. [28][29][30][31] ESI is one of the most important mass spectrometry-based methods for the analysis of molecules.…”

Section: Introductionmentioning

confidence: 99%

“…As an illustrative example of this may serve the Ag + complexation with helicenes, acting as molecular tweezers for the Ag + cation. 27 The double p-bond coordination occurs intramolecularly, preventing the addition of a second helicene molecule to the Ag + . The different geometries of the Ag + (pyridine) n complexes (with n = 1 and 2) 38,39 as opposed to the benzenecontaining counterparts 14,15 is an intriguing example of the different complexation behaviour of aza-vs. all-carbon aromatic rings.…”

Section: Introductionmentioning

confidence: 99%

Silver cation tagged on 5,7,12,14-tetraphenyl-6,13-diazapentacene and its dihydro-form

Kinzelmann,

Oschwald,

Elsen

et al. 2023

Phys. Chem. Chem. Phys.

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“…The formation of which is promoted by the strained, helical structure of the precursor ion. The [1 : 1] complexes of Ag + with the [n]helicenes (n = 6, 7) have been characterized by numerous methods, including 1 H-NMR, [43] ESI-MS, [44][45][46] X-ray [43,46] and DFT. [44][45][46][47][48] It was found that the helicene acts as a molecular tweezer in these complexes with the Ag + residing in between the terminal benzene rings.…”

Section: Introductionmentioning

confidence: 99%

Experimental and Theoretical Structure Elucidation of the [2 : 1] Complex Ion of Carbo[n]helicene with n=6, 7 and 8 and Ag⁺

et al. 2023

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Gas‐phase complexes of [n]helicenes with n = 6 ‐ 8 and the silver(I) cation are generated utilizing electrospray ionization mass spectrometry (ESI‐MS). Besides the well‐established [1:1] helicene/Ag+‐complex in which the helicene provides a tweezer‐like surrounding for the Ag+, there is also a [2:1] complex formed. Density‐functional theory (DFT) in conjunction with energy‐resolved collision‐induced dissociation (ER‐CID) experiments reveal that the second helicene attaches via π‐π stacking to the first helicene which is part of the pre‐formed [1:1] tweezer complex with Ag+. For polycyclic aromatic hydrocarbons (PAHs) of planar structure, the [2:1] complex with silver(I) is typically structured as a Ag+‐bound dimer (PAH‐‐‐Ag+‐‐‐PAH). For helicenes, the Ag+‐bound dimer is of similar thermochemical stability as the π‐π stacked dimer, however, it is kinetically inaccessible. Coronene (Cor) is investigated in comparison as an essentially planar PAH. In analogy to the π‐π stacked dimer of the helicenes, the Cor‐‐‐Ag+‐‐‐Cor‐‐‐Cor complex is also observed. Competition experiments using [n]helicene mixtures reveal that the tweezer complexes of Ag+ are preferably formed with the larger helicenes, with n = 6 being entirely ignored as the host for Ag+ in the presence of n = 7 or 8.

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Cation–π interaction of Ag+ with [6]helicene: An experimental and theoretical study

Cited by 12 publications

References 37 publications

Cation−π Interactions with Coexisting Heavy Metals Enhanced the Uptake and Accumulation of Polycyclic Aromatic Hydrocarbons in Spinach

Cation−π Interactions with Coexisting Heavy Metals Enhanced the Uptake and Accumulation of Polycyclic Aromatic Hydrocarbons in Spinach

Silver cation tagged on 5,7,12,14-tetraphenyl-6,13-diazapentacene and its dihydro-form

Experimental and Theoretical Structure Elucidation of the [2 : 1] Complex Ion of Carbo[n]helicene with n=6, 7 and 8 and Ag⁺

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Cation–π interaction of Ag+ with [6]helicene: An experimental and theoretical study

Cited by 12 publications

References 37 publications

Cation−π Interactions with Coexisting Heavy Metals Enhanced the Uptake and Accumulation of Polycyclic Aromatic Hydrocarbons in Spinach

Cation−π Interactions with Coexisting Heavy Metals Enhanced the Uptake and Accumulation of Polycyclic Aromatic Hydrocarbons in Spinach

Silver cation tagged on 5,7,12,14-tetraphenyl-6,13-diazapentacene and its dihydro-form

Experimental and Theoretical Structure Elucidation of the [2 : 1] Complex Ion of Carbo[n]helicene with n=6, 7 and 8 and Ag+

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Experimental and Theoretical Structure Elucidation of the [2 : 1] Complex Ion of Carbo[n]helicene with n=6, 7 and 8 and Ag⁺