Separation of Anionic Chlorinated Dyes from Polluted Aqueous Streams Using Ionic Liquids and Their Subsequent Recycling.

The effect of ionic liquids on the separation of chlorinated anionic dyes such as Mordant Blue 9 (MB9) or Acid Yellow 17 (AY17) via ion exchange has been investigated in model aqueous solutions that simulate wastewater from the textile dyeing industry. The effect of ionic liquids chemical nature on the separation efficiency of mentioned dyes has been compared. It was found that especially ionic liquid based on quaternary ammonium salts comprising two or three long alkyl chains bound to the quaternary ammonium nitrogen (typically benzalkonium chloride or Aliquat 336) are very effective for the separation of both studied MB9 and AY17 from aqueous solution. In addition, the innovative technique has been developed for the reactivation of spent ionic liquids which is based on the chemical reduction of the formed ion pairs using NaBH4/NiSO4, NaBH4/Na2S2O5 or Raney Al-Ni alloy/NaOH. Thus, only NaBH4/NiSO4 in co-action with Al-Ni alloy enables both effective reduction of the azo bond and subsequent hydrodechlorination of emerging chlorinated aromatic amines. The efficiency of tested dyes separation or regeneration of ion pairs was evaluated by determination of the absorbance at wavelength of the maximum absorbance, of the Chemical Oxidation Demand (COD), and of the Adsorbables Organically bound Halogens (AOX). The formation of ion pairs or products of reduction and hydrodechlorination of these ion pairs has been studied using the 1H NMR and LC-MS techniques.

Application of Raney Al-Ni Alloy for Simple Hydrodehalogenation of Diclofenac and Other Halogenated Biocidal Contaminants in Alkaline Aqueous Solution under Ambient Conditions.

Raney Al-Ni contains 62% of Ni2Al3 and 38% NiAl3 crystalline phases. Its applicability has been studied within an effective hydrodehalogenation of hardly biodegradable anti-inflammatory drug diclofenac in model aqueous concentrates and, subsequently, even in real hospital wastewater with the aim of transforming them into easily biodegradable products. In model aqueous solution, complete hydrodechlorination of 2 mM aqueous diclofenac solution (0.59 g L-1) yielding the 2-anilinophenylacetate was achieved in less than 50 min at room temperature and ambient pressure using only 9.7 g L-1 of KOH and 1.65 g L-1 of Raney Al-Ni alloy. The dissolving of Al during the hydrodehalogenation process is accompanied by complete consumption of NiAl3 crystalline phase and partial depletion of Ni2Al3. A comparison of the hydrodehalogenation ability of a mixture of diclofenac and other widely used halogenated aromatic or heterocyclic biocides in model aqueous solution using Al-Ni was performed to verify the high hydrodehalogenation activity for each of the used halogenated contaminants. Remarkably, the robustness of Al-Ni-based hydrodehalogenation was demonstrated even for the removal of non-biodegradable diclofenac in real hospital wastewater with high chloride and nitrate content. After removal of the insoluble part of the Al-Ni for subsequent hydrometallurgical recycling, the low quantity of residual Ni was removed together with insoluble Al(OH)3 obtained after neutralization of aqueous filtrate by filtration.

Highly Efficient and Controllable Methodology of the Cd0.25Zn0.75Se/ZnS Core/Shell Quantum Dots Synthesis.

The surface of any binary or multi-component nanocrystal has imperfections and defects. The number of surface defects depends both on the nature of the nanomaterial and on the method of its preparation. One of the possibilities to confine the number of surface defects is the epitaxial growth of the shell, which leads to a change in the physical properties while maintaining the morphology of the core. To form a shell of the desired thickness, an accurate calculation of the amount of its precursors is substantial to avoid the appearance of individual crystals consisting of the shell material. This study aimed to develop an effective calculation method for the theoretical amount of precursors required for the formation of a ZnS shell on the surface of a Cd0.25Zn0.75Se core, followed by the practical implementation of theoretical calculations and characterization of the prepared nanomaterials. This method allows the complete control of the masses and volumes of the initial reagents, which will in turn prevent undesirable nucleation of nuclei consisting of the shell material. In the synthesis of Cd0.25Zn0.75Se/ZnS core/shell quantum dots (QDs), the sources of chalcogens were substituted seleno- and thioureas, which are capable of not only supplanting modern toxic sources of sulfur and selenium but also allowing one to perform the controlled synthesis of highly photoluminescent QDs with a low number of surface defects. The result of this shell overcoating method was an impetuous augmentation in the photoluminescence quantum yield (PL QY up to 83%), uniformity in size and shape, and a high yield of nanomaterials. The developed synthetic technique of core/shell QDs provides a controlled growth of the shell on the core surface, which makes it possible to transfer this method to an industrial scale.

Oxidative addition of cyanogen bromide to C,N-chelated and Lappert's stannylenes.

Stannylenes of L2Sn type bearing either C,N-chelating (1, L = LCN = 2-(N,N-dimethylaminomethyl)phenyl) or bulky amido (2, L = LN = N(SiMe3)2) ligands react with cyanogen bromide (Br-C[triple bond, length as m-dash]N) via an oxidative-addition reaction to give monomeric six-coordinate (LCN)2Sn(Br)CN (1a) and four-coordinate (LN)2Sn(Br)CN (2a) stannanes in moderate yields. In solution, both 1a and 2a undergo instantaneous bromido-cyanido ligand redistribution reactions, leading to mixtures containing 1a, (LCN)2SnBr2 (1b) and (LCN)2Sn(CN)2 (1c) or 2a, (LN)2SnBr2 (2b) and (LN)2Sn(CN)2 (2c), respectively. The prepared species were characterised by multinuclear NMR spectroscopy in solution (1a-c and 2a-c) and in the solid state (1a-c). The crystal structures of 1a/b/c, 2a/b/c and sole 2b were determined by XRD analyses. DFT calculations and QTAIM analysis were also carried out to corroborate the experimental results.

Experimental and Theoretical Evidence of Spin-Orbit Heavy Atom on the Light Atom 1 H†NMR Chemical Shifts Induced through H⋠⋠⋠I- Hydrogen Bond.

Invited for the cover of this issue is the group of Michal Straka and Martin Dracínský (IOCB Prague, Czech Academy of Sciences). The image depicts a neutron star, which is used to represent the relativistic effects between a heavy element and a hydrogen atom reported in this work. Read the full text of the article at 10.1002/chem.202001532.

Experimental and Theoretical Evidence of Spin-Orbit Heavy Atom on the Light Atom 1 H†NMR Chemical Shifts Induced through H⋠⋠⋠I- Hydrogen Bond.

Spin-orbit (SO) heavy-atom on the light-atom (SO-HALA) effect is the largest relativistic effect caused by a heavy atom on its light-atom neighbors, leading, for example, to unexpected NMR chemical shifts of 1 H, 13 C, and 15 N nuclei. In this study, a combined experimental and theoretical evidence for the SO-HALA effect transmitted through hydrogen bond is presented. Solid-state NMR data for a series of 4-dimethylaminopyridine salts containing I- , Br- and Cl- counter ions were obtained experimentally and by theoretical calculations. A comparison of the experimental chemical shifts with those calculated by a standard DFT methodology without the SO contribution to the chemical shifts revealed a remarkable error of the calculated proton chemical shift of a hydrogen atom that is in close contact with the iodide anion. The addition of the relativistic SO correction in the calculations significantly improves overall agreement with the experiment and confirms the propagation of the SO-HALA effect through hydrogen bonds.

Pnictogen bonding in pyrazine•PnX5 (Pn = P, As, Sb and X = F, Cl, Br) complexes.

This paper presents a study of pnictogen bonding in a series of pyrazine•PnX5 (Pn = P, As, Sb and X = F, Cl, Br) complexes. The whole series was studied computationally. Moreover, the pyrazine complexes with PCl5 and SbCl5 were prepared and characterized experimentally. It was found that the Pn-N distances are only slightly elongated when compared to the sum of covalent radii. The conformation of PnX5 changed considerably upon the complex formation, which resulted in a significant change of the dipole moment of the PnX5 fragment and a considerably more positive σ-hole on the pnictogen atom. Finally, interaction energies were decomposed in order to provide a deeper insight into the nature of the studied pnictogen-bonded complexes. Graphical abstract The conformation of PnX5 changed considerably upon the complex formation, which resulted in a considerably more positive σ-hole on the pnictogen atom.

Sequential Camouflage of the arachno-6,9-C2B8H14 Cage by Substituents.

Sequential methylation of arachno-6,9-C2B8H14 (1) led to a series of methyl derivatives and finally to the camouflaging of all boron positions by mixed persubstitution. Thus, deprotonation of 1 produced the [arachno-6,9-C2B8H13] anion (1(-)), the methylation of which with MeI in tetrahydrofuran proceeded on the open-face boron vertexes with the formation of 5-Me-arachno-6,9-C2B8H13 (2; yield 28%) and 5,8-Me2-arachno-6,9-C2B8H12 (3; yield 36%). Observed in this reaction was also a side formation of 2-Me-closo-1,6-C2B8H9 (4; yield 6%).The electrophilic AlCl3-catalyzed CH3(+) attack of the neutral 1 in neat MeI at ambient temperature afforded 1,3-Me2-arachno-6,9-C2B8H12 (5), while a 76-h heating at 120 °C generated a mixture of the di- and triiodo derivatives 1,2,3,4,8,10-Me6-5,7-I2-arachno-6,9-C2B8H6 (6) and 1,2,3,4,7-Me5-5,7,10-I3-arachno-6,9-C2B8H6 (7). On the other hand, a HOTf-catalyzed reaction between 1 and MeOTf at reflux resulted in the isolation of 2-TfO-1,3.4,5,7,8,10-Me7-arachno-6,9-C2B8H6 (8; Tf = CF3SO2; yield 65%). The compounds were characterized by multinuclear ((11)B, (1)H, (13)C, and (19)F) NMR spectroscopy, mass spectrometry, and elemental analysis, and the structures of compounds 1, 1(-), 5, and 6 were established by X-ray diffraction analysis.

On the nature of the stabilisation of the E···π pnicogen bond in the SbCl3···toluene complex.

The off-symmetrical structure of the toluene···SbCl3 complex is a consequence of the off-centre location of σ-holes at the Sb atom. DFT-SAPT calculations have been used to determine the total interaction energies and their components. The characteristic features of the pnicogen bonding are due to the concert action of electrostatic and dispersion interactions.

Non-covalent interactions in coinage metal complexes of 1,2,4-triazole-based N-heterocyclic carbenes.

Seven coinage metal(I) complexes bearing two different triazole-based N-heterocyclic carbene (NHC) ligands, [1-tert-butyl-4-{2-[(N,N-dimethylamino)methyl]phenyl}-3-phenyl-1H-1,2,4-triazol-4-ium-5-ide and 1-tert-butyl-4-(4-methylphenyl)-3-phenyl-1H-1,2,4-triazol-4-ium-5-ide], were synthesized and fully characterized in solution by NMR spectroscopy as well as in the solid state by X-ray diffraction techniques. Furthermore, the XRD analysis showed that the bidentate coordination of the amino group substituted NHC ligand, previously observed for rhodium and palladium complexes, does not take place in the solid state structure of Au(I) complexes with various halide ligands. Nevertheless, the formation of sets of two head-to-tail oriented monomers aggregated via a weak metallophilic contact was revealed for both NHC ligands as well as for all three coinage metals with different halides. These experimental data correlate quite well with the previously published theoretical study on related complexes.

Activation of E-Cl bonds (E = C, Si, Ge and Sn) by a C,N-chelated stannylene.

The reactivity of (L(CN))(2)Sn (1) (where L(CN) is 2-(N,N-dimethylaminomethyl)phenyl-) towards various substrates containing E­Cl bond(s) has been studied (E = C, Si, Ge and Sn). Alkyl chlorides like chloroform or dichloromethane reacts with 1 to form (L(CN))(2)SnCl(2) and unidentified by-products in poor yields. The reaction of benzoyl chloride with 1 at low temperature yielded a thermally unstable product (L(CN))(2)Sn(Cl)C(O)Ph (2) which was isolated and characterized by both multinuclear NMR spectroscopy and X-ray diffraction techniques. The vicinity of the central tin atom in 2 reveals trigonal bipyramidal geometry. Attempts to oxidize 2 by dioxygen to give the corresponding organotin(IV) benzoate failed. On the other hand, the reaction of the in situ prepared (L(CN))(2)Sn=O (synthesized by the reaction of 1 with dioxygen) with PhCOCl resulted in the formation of the desired organotin(IV) benzoate (L(CN))(2)Sn(Cl)C(=O)OPh (3). The reaction of 1 with Ph3GeCl yielded triphenylgermyl-substituted diorganotin(IV) chloride (L(CN))(2)Sn(Cl)GePh(3) (4) which subsequently gave mixed diorganotin(IV) chloride-oxide [(L(CN))(2)SnCl](2)O (5) upon loss of the GePh(3) moiety in the air. When the same reaction was carried out in benzene instead of chloroform a unique [Ph(3)Ge](4)[Sn(6)O(8)] cluster (6) was obtained. Similarly, the reaction of 1 with Ph3SiCl provided triphenylsilyl-substituted diorganotin(IV) chloride (L(CN))(2)Sn(Cl)SiPh(3) (7) which was then oxidized to (L(CN))(2)Sn(Cl)OSiPh(3) (8). The unprecedented reaction of 1 with (n-Bu)(3)SnCl provided the distannane (L(CN))(2)Sn(Cl)SnBu(3) (9) which could be oxidized by dioxygen to a distannoxane (L(CN))(2)Sn(Cl)OSnBu(3) (10). In addition, the solid-state structures of 3, 5, 6 and 8 were determined by the X-ray diffraction techniques.

Direct and facile synthesis of carbon substituted alkylhydroxy derivatives of cobalt bis(1,2-dicarbollide), versatile building blocks for synthetic purposes.

Reactions of lithiated cobalt bis(1,2-dicarbollide)(1(-)) anion (1(-)) in presence of paraformaldehyde, ethylene oxide or trimethylene oxide led to the substitution of 1(-) at the C-atoms resulting in the high yield formation of monosubstituted alkylhydroxy derivatives [(1-HO(CH(2))(n)-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))-3,3'-Co(III)](-) (n = 1-3) isolated as caesium salts (Cs2, Cs3, Cs4) along with disubstituted products of general formulation [(HO(CH(2))(n)-1,2-C(2)B(9)H(10))(2)-3,3'-Co(III)](-) (n = 1-3) (Cs5, Cs6 and Cs7). Disubstituted compounds are in fact a mixture of diastereoisomers denoted as 1,1'-anti(rac-), 1,2'-syn- and in case of Cs6 and Cs7 also 1,2-vicinal-isomer, from which only the anti-isomer could be isolated in pure form in case of shorter chain compounds Cs5 and Cs6. All these alkylhydroxy derivatives can serve as versatile precursors for the generation of a variety of functional molecules. Thus, reaction of Me(3)NH4 with NaH and one equivalent of POCl(3) provided after hydrolysis the phosphorylated [(1-(HO)(2)P(O)OC(3)H(6)-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))-3,3'-Co(III)](-) derivative, isolated in the form of trimethylammonium salt, Me(3)NH8 as the main product whereas reaction with half of the equivalent produces a high yield of phosphoric acid diester (Me(3)NH)(2)9 comprising in its structure two cages connected via propyl spacers to the central part. The calcium salt Ca(10)(2) of bridged ion [µ-(HOP(O)(OC(3)H(6))(2))-(1,2-C(2)B(9)H(10))(2)-3,3'-Co(III)](-) resulted from reaction of Me(3)NH7 with NaH and one equivalent of POCl(3) followed by hydrolysis and addition of CaCl(2). All new compounds were characterized by multinuclear NMR spectroscopy and mass spectrometry and the structure of Me(3)NH3 and that of the respective salts of the pure anti-stereoisomer of dialkylhydroxy derivatives Cs5 and Me(3)NH6 were established by X-ray crystallography.

Organotin compounds: an ionophore system for fluoride ion recognition.

Ion-selective properties were established for membrane electrodes prepared by using organotin compounds of type (L(CN)RSnF2)n, (R=n-Bu (I),=Ph (II)) and (L(CN)SnF3)n (III) (L(CN)=C(6)H4(CH2NMe2)-2). Electrodes formulated with the optimized membranes containing the organotin compounds I-III as ionophores and sodium tetraphenylborate (10-30%) exhibited high selectivity for fluoride over other anions. An electrode prepared with ionophore II using dibutyl phthalate as the plasticizer and 15% sodium tetraphenylborate (NaTPB) as anion additive, possesses the best potentiometric response characteristics. It shows a detection limit of 7.9 x 10(-7) M with a slope of 62.7 mV decade(-1) of activity in buffer solutions of pH 5.5. The interference from other anions is suppressed under this optimized measurement conditions. An entirely non-Hofmeister selectivity sequence (F->CH3COO->Cl->I- approximately Br->ClO4->NO2->NO3->SCN-) with remarkable preference towards fluoride is obtained. The influence on the electrode performances by anion additive was studied, and the possible response mechanism was investigated by UV-vis spectra. The electrode has been used for direct determination of fluoride in drinking mineral water with satisfactory results.