The study of charge-transfer complexes of thiophenolates of tin and mercury with tetracyanoethylene by electronic absorption spectroscopy

Сенников, П. Г.; Tumanov, A. A.; Egorochkin, A. N.; Kravtsov, D. N.; Golovchenko, L. S.; Pombrik, S. I.

doi:10.1016/s0022-328x(00)98845-4

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“…These LMCT bands are enlightening spectroscopic reporters for the characterization and the quantification of the Hg 2+ and Cu 2+ metal complexes with L1-L3. In the case of the Hg 2+ cation, 30 2), with a S1-Hg1-S2 angle of 179.2° and Hg-S distances of 2.43 Å (Table S1, ESI †). Conversely, the [HgL2] 2+ complex displays a three-coordinate Hg 2+ ion with a T-shape coordination environment (S1-Hg1-S2, 161.5°; S1-Hg1-S3, 84.3°; S2-Hg1-S3, 84.3°) and Hg-S distances in the range of 2.59-2.81°.…”

Section: Characterisation Of the Metal Complexesmentioning

confidence: 99%

Sulphur-rich functionalized calix[4]arenes for selective complexation of Hg²⁺over Cu²⁺, Zn²⁺and Cd²⁺

et al. 2016

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The syntheses of two new ligands based on a calix[4]arene scaffold in the cone conformation functionalized on the phenolic positions 1 and 3 by diethylthiophosphonates (L1) or tetra(tri)thioethyleneglycol (L2) crowns are described. Together with ligand L3, the parent calix[4]arene substituted by a penta(tetra)thioethyleneglycol crown, the spectroscopic properties of the ligands were determined by means of UV-Vis absorption spectroscopy and steady-state and time-resolved fluorescence spectroscopy, showing that the ligands display modest but non-negligible intrinsic fluorescence properties (ϕ = 0.023; 0.026 and 0.029 for L1, L2 and L3 in CHCl, respectively). The X-ray crystal structures of ligand L1, and of its synthetic precursor were determined and analyzed for their capacity to accommodate the incoming cationic species. The ligands were further investigated for their complexation properties of divalent cations such as Cu, Zn, Hg and Cd (under their nitrate salts) in 1 : 1 CHCN/CHCl solutions (I = 0.01 M EtNNO, T = 25.0(2) °C), in which the additions of cations were monitored by absorption and steady-state fluorescence spectrophotometries. The stoichiometries of the corresponding complexes were assessed by ESI-MS, while insights into the structures of the complexes in solution were obtained with density functional theory (DFT) calculations. The influence of the sulphur and phenol coordinating moieties was addressed to show that the thiocrown compounds L2 and L3 displayed a marked affinity towards the soft mercuric cation (Δlog K ≥ 2), with no particular size selectivity effect, whereas ligand L1 can accommodate both the thio and phenol units to coordinate with Cu(ii). Altogether, these results point to the use of L3 as a selective fluoroionophore for detection of Hg.

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Section: Characterisation Of the Metal Complexesmentioning

confidence: 99%

Sulphur-rich functionalized calix[4]arenes for selective complexation of Hg²⁺over Cu²⁺, Zn²⁺and Cd²⁺

et al. 2016

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The study of charge-transfer complexes of thiophenolates of tin and mercury with tetracyanoethylene by electronic absorption spectroscopy

Cited by 1 publication

References 3 publications

Sulphur-rich functionalized calix[4]arenes for selective complexation of Hg²⁺over Cu²⁺, Zn²⁺and Cd²⁺

Sulphur-rich functionalized calix[4]arenes for selective complexation of Hg²⁺over Cu²⁺, Zn²⁺and Cd²⁺

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The study of charge-transfer complexes of thiophenolates of tin and mercury with tetracyanoethylene by electronic absorption spectroscopy

Cited by 1 publication

References 3 publications

Sulphur-rich functionalized calix[4]arenes for selective complexation of Hg2+over Cu2+, Zn2+and Cd2+

Sulphur-rich functionalized calix[4]arenes for selective complexation of Hg2+over Cu2+, Zn2+and Cd2+

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Sulphur-rich functionalized calix[4]arenes for selective complexation of Hg²⁺over Cu²⁺, Zn²⁺and Cd²⁺

Sulphur-rich functionalized calix[4]arenes for selective complexation of Hg²⁺over Cu²⁺, Zn²⁺and Cd²⁺