X-ray diffraction study of benzothiacrown compounds and their complexes with heavy metal cations

Kuz'mina, L. G.; Ведерников, А. И.; Dmitrieva, S. N.; Howard, Judith A. K.; Gromov, S. P.

doi:10.1007/s11172-007-0151-8

Cited by 9 publications

(6 citation statements)

References 17 publications

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“…This result correlates with the degree of size match between the metal ion and the macrocyclic ring and is in agreement with literature data for relevant complexes [10,15,27,28], suggesting the formation of 1:2 sandwich or 1:2 linear complexes and 1:1 (in or above the macrocyclic ring) structure arrangements with different coordination numbers (Scheme 2). This observation reflects the known variation of the Ag(I) coordination number -with a preference between 2 and 6 -depending on the ligand used [24,33].…”

Section: Discussionsupporting

confidence: 91%

Extraction Studies of Heavy Metal Ions Employing Benzothiaoxacrown Compounds

Tsend-Ayush

Wenzel

Gloe

et al. 2016

SERDJ

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Benzothiaoxacrown compounds with different numbers of sulfur and oxygen donor atoms (between 4 to 7 donors) dissolved in an organic diluent selectively extract the soft metal ions Ag(I) and Hg(II) from a mixture of Co(II), Ni(II), Cu(II), Zn(II), Ag(I) and Hg(II) present in an aqueous phase. Generally, the extraction efficiency depends on the specific structure of the benzothiaoxacrowns, on the organic diluent employed, as well as on the counter ion present in the aqueous phase. High extractions of Ag(I) and Hg(II) were achieved with all ligands from perchlorate and picrate aqueous media into nitrobenzene organic solutions. In the case of Cu(I) the extraction is significant lower; only ligand 5 with the O 2 S 4 donor atom set gives a moderate extractability. The composition of the extracted complexes depends on the crown ring size and ranges from 1:1 to 1:2 (M:L). Polarographic, UV-Vis and ESI mass spectrometric studies provide a further insight into the complex formation behavior.

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Section: Discussionsupporting

confidence: 91%

Extraction Studies of Heavy Metal Ions Employing Benzothiaoxacrown Compounds

Tsend-Ayush

Wenzel

Gloe

et al. 2016

SERDJ

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“…All the mentioned data also confirm the previously 12, 35 established features of coordination of the "soft" Hg 2+ and Ag + ions to the sulfur and oxygen atoms.…”

Section: Methodssupporting

confidence: 88%

15-Hydroxybenzomonothia-15-crown-5 with the sulfur atom linked with the benzene ring and the derived sulfoxide: synthesis, structure, and complexation with the metal cations

et al. 2010

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Novel 15 hydroxybenzomonothia 15 crown 5 containing the sulfur atom linked with the benzene ring and its S oxide were synthesized. The stability constants for the complexes of the obtained benzocrown ethers and a reference 15 hydroxybenzo 15 crown 5 with Na, Ca, Ag I , Cd, Hg II , and Pb II perchlorates were determined by 1 H NMR titration. In MeCN-d 3 , the benzothiacrown ether demonstrates a high selectivity towards the thio and oxothiophilic Hg 2+ (logK 1 = 7.1) and Pb 2+ ions (logK 1 = 7.4). In MeCN d 3 -D 2 O mixtures, the stabilities of the most of complexes decrease sharply due to competitive hydration of the metal cations except for the "soft" Ag + and Hg 2+ ions having low affinity for the "hard" oxygen atoms and, on the contrary, very high affinity for the "soft" S II atoms. This results in the change in selectivity of complexation: at the water content in solution of 20%, the benzothiacrown ether binds prefer ably the Hg 2+ (logK 1 = 5.0) and Ag + ions (logK 1 = 2.7). In MeCN d 3 , the benzothiacrown derived sulfoxide is a weak and non selective complexing agent towards all the metal cations under study; the reference 15 hydroxybenzo 15 crown 5 forms more stable complexes with the oxophilic sodium, calcium, and lead(II) cations. The conformational features of the benzocrown ethers and their metal complexes established by NMR spectroscopy and X ray diffraction are discussed. The found characteristics of the complexing ability of benzomonothia 15 crown 5 where the sulfur atom is in conjugation with the benzene ring reveal that the macrocyclic ligands with such a structure are promising as high selective and efficient complexing agents for the "soft" mercury(II) and silver(I) cations in acetonitrile-water mixtures.

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“…A classic approach to increasing target cation binding is a selection of crown ethers, which are selective and complementary to these ions. In this regard, our choice fell onto dithia-aza-crown ethers, characterized by high binding constants with mercury in various media including aqueous solutions. ,,,− Present study is devoted to the rational design of novel ultrathin films with tunable receptor properties formed by amphiphilic alkylated hemicyanine dyes with dithia-aza-crown-ether moiety. We demonstrate that the control of the monolayer structure to increase the cation-binding efficiency can be achieved not only by the traditional Langmuir monolayer technique (adjustment of spreading parameters, compression–expansion, addition of surfactant matrices, etc.)…”

Section: Introductionmentioning

confidence: 99%

Rational Design of Hemicyanine Langmuir Monolayers by Cation-Induced Preorganization of Their Structure for Sensory Response Enhancement

et al. 2018

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This study takes a novel approach to the enhancement of receptor properties of thin-film sensors based on hemicyanine dyes with dithia-aza-crown-ionophoric moiety. By means of in situ UV-vis and X-ray reflectivity (XRR) measurements, it was revealed that the introduction of up to 0.25 mmol of Hg under a preliminarily compressed monolayer, formed on pure water, does not lead to cation binding. This is due to the formation of "head-to-tail" aggregates (H-type), in which ionophoric group is blocked by the neighboring molecule. However, the presence of barium cations in the subphase under the forming Langmuir monolayer of the mentioned compound causes codirectional (head-to-head) orientation of chromoionophore fragments. This provides preorganization of a monolayer structure that facilitates the binding of complementary mercury cations, even in a compressed state: asymmetric sandwich complexes containing two dye molecules coordinate a Hg cation between them. This complex structure was confirmed by molecular modeling based on the electron density distribution calculated from XRR measurement data. Such preorganization of supramolecular ensembles induced by cations, which do not participate in the complex formation with macroheterocyclic receptors, may have applications in fields where strict control of molecular orientation at the interface is required, such as nanoelectronics, sensorics, catalysis, etc.

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X-ray diffraction study of benzothiacrown compounds and their complexes with heavy metal cations

Cited by 9 publications

References 17 publications

Extraction Studies of Heavy Metal Ions Employing Benzothiaoxacrown Compounds

Extraction Studies of Heavy Metal Ions Employing Benzothiaoxacrown Compounds

15-Hydroxybenzomonothia-15-crown-5 with the sulfur atom linked with the benzene ring and the derived sulfoxide: synthesis, structure, and complexation with the metal cations

Rational Design of Hemicyanine Langmuir Monolayers by Cation-Induced Preorganization of Their Structure for Sensory Response Enhancement

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