Conformational diversity and dynamics of distally disubstituted calix and thiacalix[4]arenes in solution

Latypov, Shamil K.; Kharlamov, Sergey V.; Muravev, Anton A.; Баландина, А. А.; Solovieva, Svetlana E.; Антипин, И. С.; Коновалов, А. И.

doi:10.1002/poc.3101

Cited by 11 publications

(7 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Given low yields of thiacalixcrowns 2b,c , alkyl fragments were firstly attached to compound 1 to access type-II/III ligands. Dialkylated products 3 and 4 were synthesized as reported previously [ 26 , 27 ] and further reacted with the glycols ( Scheme 1 ). Type-II/III crown-ethers 5b,c and 6b,c were isolated in low yields (12–32%), while yields of crown-4 5a and 6a were 75% and 39%, respectively.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined Interfaces

Muravev

Yakupov

Gerasimova

et al. 2021

IJMS

View full text Add to dashboard Cite

Understanding the interaction of ions with organic receptors in confined space is of fundamental importance and could advance nanoelectronics and sensor design. In this work, metal ion complexation of conformationally varied thiacalix[4]monocrowns bearing lower-rim hydroxy (type I), dodecyloxy (type II), or methoxy (type III) fragments was evaluated. At the liquid–liquid interface, alkylated thiacalixcrowns-5(6) selectively extract alkali metal ions according to the induced-fit concept, whereas crown-4 receptors were ineffective due to distortion of the crown-ether cavity, as predicted by quantum-chemical calculations. In type-I ligands, alkali-metal ion extraction by the solvent-accessible crown-ether cavity was prevented, which resulted in competitive Ag+ extraction by sulfide bridges. Surprisingly, amphiphilic type-I/II conjugates moderately extracted other metal ions, which was attributed to calixarene aggregation in salt aqueous phase and supported by dynamic light scattering measurements. Cation–monolayer interactions at the air–water interface were monitored by surface pressure/potential measurements and UV/visible reflection–absorption spectroscopy. Topology-varied selectivity was evidenced, towards Sr2+ (crown-4), K+ (crown-5), and Ag+ (crown-6) in type-I receptors and Na+ (crown-4), Ca2+ (crown-5), and Cs+ (crown-6) in type-II receptors. Nuclear magnetic resonance and electronic absorption spectroscopy revealed exocyclic coordination in type-I ligands and cation–π interactions in type-II ligands.

show abstract

Section: Resultsmentioning

confidence: 99%

“…Water was deionized on an Adrona Crystal purification system up to the conductivity of 0.055 µS/cm. Known procedures were employed to synthesize p-tertbutylthiacalix [4]arene 1 [56], dialkylated thiacalixarenes 3 [26] and 4 [27], and thiacalixcrowns 2a-c [24] and 6a-c [13,25].…”

Section: Methodsmentioning

confidence: 99%

Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined Interfaces

Muravev

Yakupov

Gerasimova

et al. 2021

IJMS

View full text Add to dashboard Cite

show abstract

“…We found that it is general observation for distal disubstituted thiacalix [4]arene derivatives. 27,28 Moreover, this is completely different from the behavior of disubstituted classical calix [4]arene (C[4]A) derivatives, 29 in which both O-R fragments are xed by intramolecular hydrogen bonding resulting in the rigid cup-shaped structure.…”

mentioning

confidence: 85%

“Clickable” thiacalix[4]arene derivatives bearing polymerizable 1,3-butadiyne fragments: synthesis and incorporation into polydiacetylene vesicles

et al. 2016

View full text Add to dashboard Cite

show abstract

“…It could distinguish cone and 1,3-alternate stereoisomeric forms possessing identical splitting patterns of NMR signals. In the former case, two diagonal aryl rings impose a shielding ring current effect on neighboring aryl rings, resulting in their significant upfield shift and a large spacing between these signals [18,19]. The ring current effect is impossible in the 1,3-alternate stereoisomeric form, and the aryl signals are located close to each other.…”

Section: Synthesis and Characterization Of Ligandsmentioning

confidence: 99%

Thiacalixarenes with Sulfur Functionalities at Lower Rim: Heavy Metal Ion Binding in Solution and 2D-Confined Space

Muravev

Yakupov

Gerasimova

et al. 2022

IJMS

View full text Add to dashboard Cite

Sulfur-containing groups preorganized on macrocyclic scaffolds are well suited for liquid-phase complexation of soft metal ions; however, their binding potential was not extensively studied at the air–water interface, and the effect of thioether topology on metal ion binding mechanisms under various conditions was not considered. Herein, we report the interface receptor characteristics of topologically varied thiacalixarene thioethers (linear bis-(methylthio)ethoxy derivative L2, O2S2-thiacrown-ether L3, and O2S2-bridged thiacalixtube L4). The study was conducted in bulk liquid phase and Langmuir monolayers. For all compounds, the highest liquid-phase extraction selectivity was revealed for Ag+ and Hg2+ ions vs. other soft metal ions. In thioether L2 and thiacalixtube L4, metal ion binding was evidenced by a blue shift of the band at 303 nm (for Ag+ species) and the appearance of ligand-to-metal charge transfer bands at 330–340 nm (for Hg2+ species). Theoretical calculations for thioether L2 and its Ag and Hg complexes are consistent with experimental data of UV/Vis, nuclear magnetic resonance (NMR) spectroscopy, and single-crystal X-ray diffractometry of Ag–thioether L2 complexes and Hg–thiacalixtube L4 complex for the case of coordination around the metal center involving two alkyl sulfide groups (Hg2+) or sulfur atoms on the lower rim and bridging unit (Ag+). In thiacrown L3, Ag and Hg binding by alkyl sulfide groups was suggested from changes in NMR spectra upon the addition of corresponding salts. In spite of the low ability of the thioethers to form stable Langmuir monolayers on deionized water, one might argue that the monolayers significantly expand in the presence of Hg salts in the water subphase. Hg2+ ion uptake by the Langmuir–Blodgett (LB) films of ligand L3 was proved by X-ray photoelectron spectroscopy (XPS). Together, these results demonstrate the potential of sulfide groups on the calixarene platform as receptor unit towards Hg2+ ions, which could be useful in the development of Hg2+-selective water purification systems or thin-film sensor devices.

show abstract

Conformational diversity and dynamics of distally disubstituted calix and thiacalix[4]arenes in solution

Cited by 11 publications

References 55 publications

Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined Interfaces

Switching Ion Binding Selectivity of Thiacalix[4]arene Monocrowns at Liquid–Liquid and 2D-Confined Interfaces

“Clickable” thiacalix[4]arene derivatives bearing polymerizable 1,3-butadiyne fragments: synthesis and incorporation into polydiacetylene vesicles

Thiacalixarenes with Sulfur Functionalities at Lower Rim: Heavy Metal Ion Binding in Solution and 2D-Confined Space

Contact Info

Product

Resources

About