Search Results (14)

A series of mononuclear complexes, [Fe(L5)(bylim)](BPh₄), where L5 represents a pentadentate Schiff base ligand, bylim is 1-benzyl-1-imidazole, and BPh₄⁻ is the tetraphenylborate anion, was synthesized. The determined crystal structures indicate the absence of significant cooperative interactions, which influence the properties of the eventual spin transition. Changes in magnetic behavior induced by substitution of the pentadentate ligand were investigated through magnetic susceptibility measurements. It was found that only complexes containing a non-substituted secondary amino group exhibit some form of spin crossover, whereas the majority of those with a methyl substituent remain in the high-spin state across the entire measured temperature range (2–300 K). The changes induced by the substitution of the secondary amine group were further explored through theoretical calculations at DFT and CASSCF/NEVPT2 levels of theory. The topology and energetics of electron density and atomic charges were investigated through QT-AIM calculations. Full article

A cyclobenzaprine-tetraphenylborate (CBP-TPB) complex was synthesized, achieving a 78% yield through an anion exchange reaction. The white crystals of the complex were formed in acetonitrile and characterized using a variety of spectroscopic and analytical techniques, including ultraviolet, infrared, mass, elemental, and nuclear magnetic resonance (NMR) spectroscopy, as well as X-ray crystallography. The study employed a comprehensive approach to investigate the structural properties, stability, and behavior of the CBP-TPB complex. The use of crystallographic analysis, Hirshfeld surface analysis, quantum theory of atoms in molecules, noncovalent interaction reduced density gradient, global reactivity descriptors, frontier molecular orbitals, molecular electrostatic potential, and ultraviolet-visible spectroscopy provided valuable insights into the complex’s molecular geometries, supramolecular features, and intermolecular interactions. These findings contribute to a better understanding of the CBP-TPB complex’s potential applications in fields such as pharmaceuticals and materials science and emphasize the importance of combining theoretical predictions and experimental measurements in understanding molecular properties. The study also demonstrated the potential of density functional theory-based computational methods for predicting NMR spectroscopic parameters. Full article

The continuously increasing flow of toxic heavy metals to the environment due to intensive industrial activity and tightening requirements with regard to the content of metal ions in drinking and discharged waters urges the development of affordable and sensitive devices to the field control of pollutants. Here, we report a new thiated Rhodamine-lactam probe for Hg²⁺ detection and demonstrate how its sensitivity can be increased via the incorporation of the probe molecules into the optically transparent siloxane-acrylate coatings on polymethyl methacrylate and, alternatively, into the water-dispersible light-harvesting FRET nanoparticles (NPs), in which dye cations are separated by fluorinated tetraphenylborate anions. We have shown that the optimization of the FRET NPs composition had allowed it to reach the antenna effect of ~300 and fabricate “off/on” sensor for Hg²⁺ ion determination in aqueous solutions with the detection limit of ~100 pM, which is far below the maximum permissible concentration (MPC) of mercury in drinking water recommended by the World Health Organization. Although this work is more proof-of-concept than a ready-to-use analytical procedure, the suggested approaches to fabrication of the FRET NPs based on the popular rhodamine-lactam platform can be used as a background for the development of low-cost portable sensing devices for the extra-laboratory determination of hazardous metal ions. Full article

The series of substituted 1,2,4-selenodiazolium tetraphenylborate complexes were synthesized via cyclization between 2-pyridylselenylchloride, followed by the anion metathesis, and fully characterized. The utilization of tetraphenylborate anion, a strong π-electron donor via its phenyl rings, promoted the formation of assemblies exhibiting selenium–π interactions. The chalcogen bonding (ChB) interactions involving the π-systems of the tetraphenylborate anion were studied using density functional theory (DFT) calculations, where “mutated” anions were used to estimate the strength of the Se···π chalcogen bonds. Moreover, molecular electrostatic potential (MEP) surfaces were used to investigate the electron-rich and poor regions of the ion pairs. The quantum theory of atoms-in-molecules (QTAIM) and the noncovalent interaction (NCI) plot methods based on the topology of the electron density were used and combined to characterize the ChBs. The investigation reported herein disclosed that the formation of symmetrical dimers can be broken by the introduction of a stronger π-acceptor and, consequently, forming stronger Se···π contacts with selenodiazolium cations. Full article

As anionic surfactants are used as cleaning agents, they pose an environmental and health threat. A novel potentiometric sensor for anionic surfactants based on the 1,3-dioctadecyl-1H-imidazol-3-ium tetraphenylborate (DODI–TPB) ionophore is presented. The newly developed approach for DODI–TPB synthesis is faster and simpler than the currently used strategies and follows the green chemistry principles. The DODI–TPB ionophore was characterized by computational and instrumental techniques (NMR, LC–MS, FTIR, elemental analysis) and used to produce a PVC-based DODI–TPB sensor. The sensor showed linear response to dodecylbenzenesulfonate and dodecyl sulfate in concentration ranges of 6.3 × 10⁻⁷–3.2 × 10⁻⁴ M and 5.9 × 10⁻⁷–4.1 × 10⁻³ M, for DBS and SDS, respectively. The sensor exhibits a Nernstian slope (59.3 mV/decade and 58.3 mV/decade for DBS and SDS, respectively) and low detection limits (7.1 × 10⁻⁷ M and 6.8 × 10⁻⁷ M for DBS and SDS, respectively). The DODI–TPB sensor was successfully tested on real samples of commercial detergents and the results are in agreement with the referent methods. A computational analysis underlined the importance of long alkyl chains in DODI⁺ and their C–H∙∙∙π interactions with TPB⁻ for the ionophore formation in solution, thereby providing guidelines for the future design of efficient potentiometric sensors. Full article

Europium bis(tetraphenylborate) [Eu(thf)₇][BPh₄]₂⋅thf containing a fully solvated [Eu(thf)₇]²⁺ cation, was synthesized by protolysis of “EuPh₂” (from Eu and HgPh₂) with Et₃NHBPh₄, and the structure was determined by single-crystal X-ray diffraction. Efforts to characterize the putative “Ph₂Ln” (Ln = Eu, Yb) reagents led to the synthesis of a mixed-valence complex, [(thf)₃Yb^II(μ-Ph)₃Yb^III(Ph)₂(thf)]⋅2thf, resulting from the reaction of Yb metal with HgPh₂ at a low temperature. This mixed-valence Yb^II/Yb^III compound was studied by ¹⁷¹Yb-NMR spectroscopy and single-crystal X-ray diffraction, and the oxidation states of the Yb atoms were assigned. Full article

An experimentally simple method for the direct determination of single-ion partition coefficients between water and a PVC membrane plasticized with o-NPOE is suggested. The method uses the traditional assumption of equal single-ion partition coefficients for some reference cation and anion, in this case tetraphenylphosphonium (TPP⁺) and tetraphenylborate (TPB⁻). The method is based on an integrated approach, including direct study of some salts’ distribution between water and membrane phases, estimation of ion association constants, and measurements of unbiased selectivity coefficients for ions of interest, including the reference ones. The knowledge of distribution coefficients together with ion association constants allows for direct calculation of the multiple of the single-ion partition coefficients for the corresponding cation and anion, while the knowledge of unbiased selectivity coefficients together with ion association constants allows for immediate estimation of the single-ion partition coefficients for any ion under study, if the corresponding value for the reference ion is known. Both potentiometric and extraction studies are inherently equilibrium-based techniques, while traditionally accepted methods such as voltammetry and diffusion are kinetical. The inner coherent scale of single-ion partition coefficients between water and membrane phases was constructed. Full article

The synthesis and structural characterization of a series of supramolecular complexes of bicyclic cationic pyridine-fused 1,2,4-selenodiazoles with various anions is reported. The binding of trifluoroacetate, tetrachloroaurate, tetraphenylborate, perrhenate, and pertechnetate anions in the solid state is regarded. All the anions interact with selenodiazolium cations exclusively via a pair of “chelating” Se⋯O and H⋯O non-covalent interactions, which make them an attractive, novel, non-classical supramolecular recognition unit or a synthon. Trifluoroacetate salts were conveniently generated via novel oxidation reaction of 2,2′-dipyridyl diselenide with bis(trifluoroacetoxy)iodo)benzene in the presence of corresponding nitriles. Isolation and structural characterization of transient 2-pyridylselenyl trifluoroacetate was achieved. X-ray analysis has demonstrated that the latter forms dimers in the solid state featuring very short and strong Se⋯O and Se⋯N ChB contacts. 1,2,4-Selenodiazolium trifluoroacetates or halides show good solubility in water. In contrast, (AuCl₄)⁻, (ReO₄)⁻, or (TcO₄)⁻ derivatives immediately precipitate from aqueous solutions. Structural features of these supramolecular complexes in the solid state are discussed. The nature and energies of the non-covalent interactions in novel assembles were studied by the theoretical methods. To the best of our knowledge, this is the first study that regards perrhenate and pertechnetate as acceptors in ChB interactions. The results presented here will be useful for further developments in anion recognition and precipitation involving cationic 1,2,4-selenodiazoles. Full article

The title compound tetraphenylborate salt of clonidine (Catapres^®), 2-(2,6-dichlorophenylamino)-2-imidazoline tetraphenylborate (3), was prepared in 76 % yield by the reaction of 2-(2,6-dichlorophenylamino)-2-imidazoline hydrochloride (clonidine hydrochloride) (1) with sodium tetraphenylborate (2) in deionized water through anion exchange reaction at ambient temperature. The structure of the title borate salt was characterized by UV, thermal analysis, mass and NMR analyses. White crystals of (3) suitable for an X-ray structural analysis were obtained by slow growing from acetonitrile. The molecular structure of the titled compound (3) was crystallized in the acetonitrile, P2₁/c, a = 9.151 (3) Å, b = 12.522 (3) Å, c = 25.493 (6) Å, β = 105.161 (13)° V = 2819.5 (13) ų, Z = 4. A DFT quantum chemistry calculation method was employed to investigate the interaction mechanism of clonidine with tetraphenylborate. The stable configurations of the complexes of clonidine with tetraphenylborate with electrostatic interactions were obtained. Finally, the interaction strength and type of the complexes were studied through the reduced density gradient (RDG) function. This study provides new theoretical insight into the interaction mechanism and a guide for screening and designing the optimal clonidine and tetraphenylborate reacting to form the complex. Full article

A 1,3-dihexadecyl-1H-benzo[d]imidazol-3-ium-tetraphenylborate (DHBI-TPB) ion-pair implemented in DHBI-TPB surfactant sensor was used for the potentiometric quantification of anionic surfactants in detergents and commercial household care products. The DHBI-TPB ion-pair was characterized by FTIR spectroscopy and computational analysis which revealed a crucial contribution of the C–H∙∙∙π contacts for the optimal complex formation. The DHBI-TPB sensor potentiometric response showed excellent analytical properties and Nernstian slope for SDS (60.1 mV/decade) with LOD 3.2 × 10⁻⁷ M; and DBS (58.4 mV/decade) with LOD 6.1 × 10⁻⁷ M was obtained. The sensor possesses exceptional resistance to different organic and inorganic interferences in broad pH (2–10) range. DMIC used as a titrant demonstrated superior analytical performances for potentiometric titrations of SDS, compared to other tested cationic surfactants (DMIC > CTAB > CPC > Hyamine 1622). The combination of DHBI-TPB sensor and DMIC was successfully employed to perform titrations of the highly soluble alkane sulfonate homologues. Nonionic surfactants (increased concentration and number of EO groups) had a negative impact on anionic surfactant titration curves and a signal change. The DHBI-TPB sensor was effectively employed for the determination of technical grade anionic surfactants presenting the recoveries from 99.5 to 101.3%. The sensor was applied on twelve powered samples as well as liquid-gel and handwashing home care detergents containing anionic surfactants. The obtained results showed good agreement compared to the outcomes measured by ISE surfactant sensor and a two-phase titration method. The developed DHBI-TPB surfactant sensor could be used for quality control in industry and has great potential in environmental monitoring. Full article

A novel promising carbon paste electrode with excellent potentiometric properties was prepared for the analysis of trihexyphenidyl hydrochloride (THP), the acetylcholine receptor and an anticholinergic drug in real samples. It contains 10.2% trihexyphenidy-tetraphenylborate ionic pair as the electroactive material, with the addition of 3.9% reduced graphene oxide and 0.3% of anionic additive into the paste, which consists of 45.0% dibutylphthalate as the solvent mediator and 40.6% graphite. Under the optimized experimental conditions, the electrode showed a Nernstian slope of 58.9 ± 0.2 mV/decade with a regression coefficient of 0.9992. It exhibited high selectivity and reproducibility as well as a fast and linear dynamic response range from 4.0 × 10⁻⁷ to 1.0 × 10⁻² M. The electrode remained usable for up to 19 days. Analytical applications showed excellent recoveries ranging from 96.8 to 101.7%, LOD was 2.5 × 10⁻⁷ M. The electrode was successfully used for THP analysis of pharmaceutical and biological samples. Full article

Two manganese(III) porphyrins: manganese(III) tetraphenylporphyrin chloride and manganese(III)-tetrakis(3-hydroxyphenyl)porphyrin chloride were tested as ionophores for the construction of new diclofenac−selective electrodes. The electroactive material was incorporated either in PVC or a sol−gel matrix. The effect of different plasticizers and additives (anionic and cationic) on the potentiometric response was studied. The best results were obtained for the PVC membrane plasticized with dioctylphtalate and having sodium tetraphenylborate as a lipophilic anionic additive incorporated. The sensor response was linear in the concentration range 3 × 10⁻⁶ – 1 × 10⁻² M with a slope of −59.7 mV/dec diclofenac, a detection limit of 1.5 × 10⁻⁶ M and very good selectivity coefficients. It was used for the determination of diclofenac in pharmaceutical preparations, by direct potentiometry. The results were compared with those obtained by the HPLC reference method and a good agreement was found between the two methods. Full article

Poly vinylchloride (PVC) based membranes of 4,4',4'',4'''-21H,23H-porphine–5,10,15,20 –tetrayl) tetrakis (benzoic acid) (TBAP) and 2,3,7,8,12,13,17,18-octamethyl - 21H, 23H-porphine (OMP) were prepared using dibutyl phthalate (DBP), dioctylphthalate (DOP), dibutyl(butyl)phosphonate (DBBP) and 1-chloronaphthalene (CN) as plastcizing solvent mediators and sodium tetraphenylborate (NaTPB) as an anion excluder for Ni²⁺ selective sensors. TBAP based membrane exhibits linearity over a wide concentration range 2.0x10^-6–1.0x10^-1M (0.12 – 5.8x10³ppm) with a slope of 29.6 mV/decade of activity while OMP based membrane showed linear potential response in the concentration range 1.0x10^-5 –1.0x 10^-1M (0.60 – 5.8x10³ppm) with a Nernstian slope of 29.0 mV/decade of activity. The electrode assembly works between pH 2.0 – 7.0, exhibits a fast response time of 10-15s and performed satisfactorily over a period of six months with good reproducibility. Excellent selectivity of the order of 10^-3 over a number of cations and quantitative determination of Ni²⁺ in effluents discharged from electroplating industry demonstrates the utility of the proposed sensor. The electrode assembly was also used as an indicator electrode in the potentiometric titration of Ni²⁺ with EDTA. Full article

The tetramethyldibenzocyclam derivative, was synthesized and characterized and was used for fabrication of potentiometric sensor for Ni²⁺ metal ion. 5,7,8,14-tetramethyldibenzo[b,i]-1,4,8,11-tetrazacyclotetradecanenickel(II)chloride, ([Ni(Me₄Bzo₂[14]ane N₄)]Cl₂) (II) was obtained in good yield as orange red salt by Fe/HCl reduction of the corresponding tetraazaannulene complex [Ni(Me4Bzo₂taa)], (I). Membrane having [Ni(Me₄Bzo₂[14]aneN₄)]Cl₂ (II) as electroactive material, sodium tetraphenylborate (NaTPB) as an anion discriminator, dibutyl butylphosphonate (DBBP) as plasticizer in PVC matrix in the percentage ratio 5.0:2.5:200:200 (II:NaTPB:DBBP:PVC)(w/w) exhibits a linear response to Ni²⁺ in the concentration range 7.0×10^-6- 1.0×10^-1M with a slope of 29.8±0.2 mV/decade of activity and a fast response time of 12s. The sensor works well in the pH range 2.0-7.6 and can be satisfactorily used in presence of 40% (v/v) methanol, ethanol or acetone. The sensor is highly selective for Ni²⁺ over a large number of mono-, biand trivalent cations. The sensor has been successfully used as indicator electrode in the potentiometric titration of Ni²⁺ against EDTA. These electrodes can be used to determine the concentration of Ni²⁺ in real samples. Full article