[6]Helicene as a novel molecular tweezer for the univalent silver cation: Experimental and theoretical study

Klepetářová, Blanka; Makrlík, Emanuel; Dytrtová, Jana Jaklová; Böhm, Stanislav; Vaňura, Petr; Storch, Jan

doi:10.1016/j.molstruc.2015.04.022

Cited by 11 publications

(2 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, the binding of the silver particle in the focal cavity of hexahelicene has been exhibited, given that the counter ion is quickly coordinating. In this coupling mode, the hexahelicene is working as a chiral molecular tweezer of silver but the resulting bond is not strong and the formed complex is not stable [18, 19].…”

Section: Introductionmentioning

confidence: 99%

Application of Innovative Analytical Modeling for the Physicochemical Analysis of Adsorption Isotherms of Silver Nitrate on Helicenes: Phenomenological Study of the Complexation Process

Souissi

Yahia

2021

Adsorption Science & Technology

View full text Add to dashboard Cite

The interaction between the silver ion and the cyclic aromatic molecules, namely, the helicenes, is the subject of this paper. In fact, a silver complexation system based on quartz crystal microbalance (QCM) sensor with a functional film of helicenes has been designed and developed at four temperatures. The developed system, in which the sensor response reflects the adsorption of the hexahelicene and the heptahelicene, was able to control the complexed mass of silver for each concentration. Experimental outcomes indicated that the quartz crystal coated with heptahelicene is the adequate material for silver adsorption. Then, a theoretical study has been performed through two statistical physics models (SMPG and SMRG) in order to analyze the experimental adsorption isotherms of the two helicenes at the ionic scale. The SMRG model was developed using the real gas law and was satisfactorily applied for the microscopic investigation of the hexahelicene isotherms indicating that the lateral interactions between the adsorbates are responsible of the decrease of the adsorbed quantity at saturation. The interpretation of the two models’ parameters indicated that the adsorption of the two helicenes is an endothermic phenomenon. Interestingly, the heptahelicene is recommended for silver complexation because it shows the highest adsorption energies involving chemical bonds during the complexation process. The SMPG model and the SMRG model also allow prediction of three thermodynamic functions (configurational entropy, Gibbs free enthalpy, and internal energy) which govern the adsorption mechanism of silver on the two helicenes.

show abstract

Section: Introductionmentioning

confidence: 99%

Application of Innovative Analytical Modeling for the Physicochemical Analysis of Adsorption Isotherms of Silver Nitrate on Helicenes: Phenomenological Study of the Complexation Process

Souissi

Yahia

2021

Adsorption Science & Technology

View full text Add to dashboard Cite

show abstract

“…The formation of metal complexes from helicenes dates back from the research envisioned by the early work of Katz, with the aim to incorporate several metallic centers in metallocene structure showing η 5 /η 3 hapticity . Recently, the formation of cation−π complexes with [6]‐ and [7]helicene involving Ag(I), extends the usage of different transition metals in the formation of helicene complexes as usually reserved for Fe, Co, Ru, Ir, among others,,,, allowing an increasing knowledge in the formation of polyaromatic receptor for metallic cations, where the bonding and mobility of alkali metals has been recently evaluated computationally . Such capability is of relevance due to their potential importance in the areas of metal‐ion sensing, electrical conductors, and photoresponsive devices to name a few .…”

Section: Introductionmentioning

confidence: 99%

Helicenes as Molecular Tweezers in the Formation of Cation−π Complexes. Bonding and Circular Dichroism Properties from Relativistic DFT Calculations

et al. 2018

View full text Add to dashboard Cite

Helicene ligands possess a unique helicoidal π-conjugated framework providing high optical rotation values. This has stimulated a growing interest in helicene derivatives as building blocks, which has triggered the development of simple strategies to tune their properties. In this context, we evaluated the formation of cation-π complexes derived from [6]- and [7]helicene, involving Sn , Cd , and In in addition of Ag , which appears as a plausible modification of such helicoidal structure. The nature of the cation-π interaction in the studied helicene complexes exhibits a covalent character, accounting for ligand π-donation to 5 s and 5p empty orbitals of the involved cations. Furthermore, the evaluation of their optical activity exhibits notorious modification patterns in the circular dichroism spectrum, suggesting that the modifications of the optical activity are dependent on the nature of the cation and its related charge state. Thus, the plausible formation of new cation-π complexes derived from helicene ligands, as discussed here, may lead to the characterization of novel species expanding the chemistry of helicene metal complexes to even to larger helicene units. We believe that the present study may open new avenues in the formation of cation-π helicene complexes.

show abstract

Reactivity and Transformations

Chen

Shen

2016

Helicene Chemistry

View full text Add to dashboard Cite

[6]Helicene as a novel molecular tweezer for the univalent silver cation: Experimental and theoretical study

Cited by 11 publications

References 42 publications

Application of Innovative Analytical Modeling for the Physicochemical Analysis of Adsorption Isotherms of Silver Nitrate on Helicenes: Phenomenological Study of the Complexation Process

Application of Innovative Analytical Modeling for the Physicochemical Analysis of Adsorption Isotherms of Silver Nitrate on Helicenes: Phenomenological Study of the Complexation Process

Helicenes as Molecular Tweezers in the Formation of Cation−π Complexes. Bonding and Circular Dichroism Properties from Relativistic DFT Calculations

Reactivity and Transformations

Contact Info

Product

Resources

About