Experimental and Theoretical Investigation on the Extractive Mass Transfer of Eu3+ Ions Using Novel Amide Ligands in 1-Hexyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide.

Novel amide ligands in the ionic liquid (1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) were utilized for the liquid-liquid biphasic mass transfer of Eu3+ ions from aqueous acidic waste solution. The cation exchange mechanism was found to be operative with the formation of [Eu(NO3)2L3]+ species (L = 4-chloro-N-(1-methyl-1H-pyrazol-3-yl)picolinamide). However, the presence of an inner-sphere water molecule was revealed by density functional theory (DFT) calculations. The viscosity-induced slower kinetics was evidenced during mass transfer, which was improved by increasing temperature. The process was exothermic in nature. The improvement in the kinetics of extractive mass transfer at higher temperatures is evinced by a reduction in the distribution ratio value. The spontaneity of the reaction was evidenced through the negative Gibbs free energy value, whereas the process enhances the entropy of the system, probably by releasing water molecules at least partially during complexation. The structures of bare ligands and complexes have been optimized by using DFT calculations. A high value of complexation energy, solvation energy, and associated enthalpy and free energy change reveal the efficacy in binding Eu with O and N donor atoms. In addition, natural population analysis, atoms-in-molecules analysis, and energy decomposition analysis have been employed to explore the nature of bonding existing in Eu-O and Eu-N bonds.

Selective recognition and extraction of arsenate by a urea-functionalized tripodal receptor from competitive aqueous media.

A second-generation hydrogen bond donor (HBD) anion receptor with an inner amide cavity and an outer urea cavity can selectively and efficiently extract arsenate (AsO43-) from water in the presence of competitive oxoanions and halides. The X-ray structure showed encapsulation of AsO43- in a π-stacked dimeric capsular assembly of the receptor, the first crystallography-based example of pentavalent AsO43- trianion recognition by a HBD receptor.

Why intermolecular nitric oxide (NO) transfer? Exploring the factors and mechanistic aspects of NO transfer reaction.

Small molecule activation and their transfer reactions in biological or catalytic reactions are greatly influenced by the metal-centers and the ligand frameworks. Here, we report the metal-directed nitric oxide (NO) transfer chemistry in low-spin mononuclear {Co(NO)}8, [(12-TMC)CoIII(NO-)]2+ (1-CoNO, S = 0), and {Cr(NO)}5, ([(BPMEN)Cr(NO)(Cl)]+) (4-CrNO, S = 1/2) complexes. 1-CoNO transfers its bound NO moiety to a high-spin [(BPMEN)CrII(Cl2)] (2-Cr, S = 2) and generates 4-CrNOvia an associative pathway; however, we did not observe the reverse reaction, i.e., NO transfer from 4-CrNO to low-spin [(12-TMC)CoII]2+ (3-Co, S = 1/2). Spectral titration for NO transfer reaction between 1-CoNO and 2-Cr confirmed 1 : 1 reaction stoichiometry. The NO transfer rate was found to be independent of 2-Cr, suggesting the presence of an intermediate species, which was further supported experimentally and theoretically. The experimental and theoretical observations support the formation of µ-NO bridged intermediate species ({Cr-NO-Co}4+). Mechanistic investigations using 15N-labeled-15NO and tracking the 15N-atom established that the NO moiety in 4-CrNO is derived from 1-CoNO. Further, to investigate the factors deciding the NO transfer reactivity, we explored the NO transfer reaction between another high-spin CrII-complex, [(12-TMC)CrII(Cl)]+ (5-Cr, S = 2), and 1-CoNO, showing the generation of the low-spin [(12-TMC)Cr(NO)(Cl)]+ (6-CrNO, S = 1/2); however, again there was no opposite reaction, i.e., from Cr-center to Co-center. The above results advocate clearly that the NO transfer from Co-center generates thermally stable and low-spin and inert {Cr(NO)}5 complexes (4-CrNO & 6-CrNO) from high-spin and labile Cr-complexes (2-Cr & 5-Cr), suggesting a metal-directed NO transfer (cobalt to chromium, not chromium to cobalt). These results explicitly highlight that the NO transfer is strongly influenced by the labile/inert behavior of the metal-centers and/or thermal stability rather than the ligand architecture.

Construction of Pyrazine-Appended 1D and 3D Cobalt(II) Succinate Coordination Polymers: Influence of Solvent on Architectures and Applications in Gas Adsorption and NAC Detection.

An underexplored reaction of pyrazine (rigid and linear) and succinic acid (flexible) with Co(NO3)2·6H2O afforded four new coordination polymers (CPs): [Co(H2O)(pyz)(suc)] (1), [Co(H2O)2(pyz)(suc)] (2), [Co(H2O)4(pyz)](suc) (3) and [Co2(H2O)2(pyz)(suc)2] (4), as well as [Co(HCO2)2(pyz)] (5) being lately reported along with well-known 6 and 7. The CPs were obtained as stable crystalline materials and characterized by conventional solid-state techniques, including X-ray crystallography. Hydrothermally produced compounds 1 and 2 were both 3D CPs. While 3 and 4 obtained under ambient/solvothermal conditions in DMSO generated 1D and 3D structures, 5 isolated from DMF under solvothermal conditions had a 3D structure. The topologies of the coordination polymers 1-7 were described by underlying nets 3D 5-c fet, 3D 4-c cds, 1D 2-c 2C1, 3D 5-c bnn, 3D 6-c rob, 1D 2-c 2C1, and 3D 6-c pcu, respectively. The plot of χM -1 versus T was essentially linear in the entire temperature range following the Curie-Weiss law with a Curie constant (C) of 2.525 and a negative Weiss constant (ϕ) of -46.24 K, suggesting weak antiferromagnetic (AF) exchange interactions. CO2 and N2 adsorption studies of 1-5 featured type III isotherms. 1 was found to show remarkably higher quenching efficiencies for nitrophenols (η = 98% for o-NP) over other NACs. The Stern-Volmer plot exhibited deviation in linearity with K sv values about 200 times greater than that for the simplest nitroaromatic compound (NB), signifying its exclusive quenching ability toward 1. The LOD for p-NP addition to 1 was found to be 0.995 ppm.

1,6-Addition of 1,2,3-NH triazoles to para-quinone methides: Facile access to highly selective N1 and N2 substituted triazoles.

The regioselective syntheses of N1 and N2 substituted triazoles through a 1,6-addition reaction of 1,2,3-NH triazoles to p-quinone methide were achieved under mild reaction conditions. The present reactions showed superior results in terms of selectivity, mild reaction conditions, short reaction time and broad substrate scope with good functional-group compatibility. Considering the high synthetic value of N1- and N2-substituted compounds and p-QM related research, the present strategy will greatly benefit researchers in various fields.

A side-on Mn(III)-peroxo supported by a non-heme pentadentate N3Py2 ligand: synthesis, characterization and reactivity studies.

A mononuclear manganese(iii)-peroxo complex [MnIII(N3Py2)(O2)]+ (1a) bearing a non-heme N,N'-dimethyl-N-(2-(methyl(pyridin-2-ylmethyl)amino)ethyl)-N'-(pyridin-2-ylmethyl)ethane-1,2-diamine (N3Py2) ligand was synthesized by the reaction of [Mn(N3Py2)(H2O)](ClO4)2 (1) with hydrogen peroxide and triethylamine in CH3CN at 25 °C. The reactivity of 1a in aldehyde deformylation using 2-phenyl propionaldehyde (2-PPA) was studied and the reaction kinetics was monitored by UV-visible spectroscopy. A kinetic isotope effect (KIE) = 1.7 was obtained in the reaction of 1a with 2-PPA and α-[D1]-PPA, suggesting nucleophilic character of 1a. The activation parameters ΔH‡ and ΔS‡ were determined using the Eyring plot while Ea was obtained from the Arrhenius equation by performing the reaction between 288 and 303 K. Hammett constants (σp) of para-substituted benzaldehydes p-X-Ph-CHO (X = Cl, F, H, and Me) were linear with a slope (ρ) = 3.0. Computational study suggested that the side-on structure of 1a is more favored over the end-on structure and facilitates the reactivity of 1a.

Revisiting salicylidene-based anion receptors.

Several salicylidene-based colorimetric and fluorimetric anion sensors are known in the literature. However, our 1H-NMR experimental results (in DMSO-d6) showed hydrolysis of imine (-N[double bond, length as m-dash]CH-) bonds in salicylidene-based receptors (SL, CL1 and CL2) in the presence of quaternary ammonium salts (n-Bu4N+) of halides (Cl- and Br-) and oxo-anions (H2PO4 -, HSO4 - and CH3COO-). The mono-salicylidene compound CL1 showed the most extensive -N[double bond, length as m-dash]CH- bond hydrolysis in the presence of anions. In contrast, the di-salicylidene compound CL2 and the tris-salicylidene compound SL showed comparatively slow hydrolysis of -N[double bond, length as m-dash]CH- bonds in the presence of anions. Anion-induced imine bond cleavage in salicylidene compounds could easily be detected in 1H-NMR due to the appearance of the salicylaldehyde -CHO peak at 10.3 ppm which eventually became more intense over time, and the -N[double bond, length as m-dash]CH- peak at 8.9-9.0 ppm became considerably weaker. Furthermore, the formation of the salicylidene O-H⋯X- (X- = Cl-/Br-) hydrogen-bonded complex, peak broadening due to proton-exchange processes and keto-enol tautomerism have also been clearly observed in the 1H-NMR experiments. Control 1H-NMR experiments revealed that the presence of moisture in the organic solvents could result in gradual hydrolysis of the salicylidene compounds, and the rate of hydrolysis has further been enhanced significantly in the presence of an anion. Based on 1H-NMR results, we have proposed a general mechanism for the anion-induced hydrolysis of imine bonds in salicylidene-based receptors.

Di-µ-aqua-bis-[aqua-(2,2'-bi-pyridine)(4-nitro-benzoato)cobalt(II)] bis-(4-nitro-benzoate).

The title compound, [Co2(C7H4NO4)2(C10H8N2)2(H2O)4](C7H4NO4)2, consists of a centrosymmetric bimetallic complex charge-balanced by free 4-nitro-benzoate anions. The CoII ion exhibits a distorted cis-CoN2O4 octa-hedral coordination environment and the Co⋯Co separation is 3.326 (2) Å. In the crystal, the dications and anions are linked by O-H⋯O and C-H⋯O hydrogen bonds.