P-toluenesulfonate Ion Research Articles

Natural degradation of polypyrrole nanowires in NaOH solutions and its degradation kinetics

The polypyrrole (PPy) nanowires doped with p-toluenesulfonate ions (PPy/pTS NWs) are prepared and degraded in aerated and deaerated NaOH solutions (CNaOH=0.02 - 0.5 M) for different times to examine their natural degradation behavior and kinetics. After degradation, the fluffy PPy/pTS NWs network film generally exhibits a uniform natural degradation state with apparent damaged areas on the nanowires' surface, decreased nanowire diameter, and increased film thickness. The electroactivity degradation of PPy/pTS NWs still follows the first-order degradation kinetics, like the bulk-structured PPy/pTS films. The natural degradation kinetics model established from the bulk-structured PPy films is proven to apply to PPy/pTS NWs. The rate equations for the chemical and electrochemical degradation of PPy/pTS NWs in NaOH solutions are determined. Additionally, it is confirmed that the electrochemical degradation process is the dominant factor, while CNaOH significantly impacts the chemical degradation process. The structural features of PPy/pTS NWs do not alter the chemical and electrochemical degradation processes but significantly accelerate the degradation rates. This research will contribute to our understanding of the degradation kinetics of PPy nanomaterials and support their practical applications.

Effect of counter anion on the uniformity, morphology and electrochromic properties of electrodeposited poly(3,4-ethylenedioxythiophene) film

Poly (3,4-ethylenedioxythiophene) (PEDOT) films were successfully deposited on fluorine-doped tin oxide (FTO) glass, through a facile electropolymerization process in aqueous solutions containing Cl−, p-toluenesulfonate ion (TsO−), NO3− or ClO4−. The influences of the counter anion in the electrolyte on the uniformity, morphology and electrochromic properties of the obtained PEDOT films were investigated. Scanning electron microscopy (SEM) was employed to characterize the morphology of the as-deposited films. Electrochemical measurements and ultraviolet–visible (UV–Vis) transmittance spectra were applied to investigate the electrochromic properties of PEDOT films, and the compositions of the films were studied by X-ray photoelectron spectroscopy (XPS). It has been demonstrated that the anion in the electrolyte during the electropolymerization process directly influences the uniformity, morphology and electrochromic performance of PEDOT films. The films prepared in Cl− possess a microstructure with poor uniformity, and present a unique bright blue/brown transition during the oxidation/reduction cycles, while that prepared in TsO−, NO3− and ClO4− consist of hierarchical submicroflowers, nanonetworks and submicroparticles, respectively, and all of them show sky blue/purple transition. The electrochromism process of PEDOT films are accompanied by insertion and extraction of ClO4−. Additionally, the maximum contrast, switching time and cycle life of the films are found to be varied with the counter anion.

A solid-state [2 + 2] photodimerization involving coordination of Ag(I) ions to 2-pyridyl groups

Photoreactive Ag(I) complexes of p-toluenesulfonate ions with the unsymmetrical alkene trans-1-(4-acetoxyphenyl)-2-(2-pyridyl)ethylene 1 is reported. The crystal [Ag(p-tol)(1)2]•(H2O) (p-tol = p-toluenesulfonate) undergoes a [2 + 2] photocycloaddition reaction in quantitative yield to afford the head-to-tail (ht) photoproduct rctt-1,3-bis(2-pyridyl)-2,4-bis(4-acetoxyphenyl)cyclobutane 2 regioselectively. The aromatic rings of the olefin participate in face-to-face π–π interactions and adopt an anti-conformation to position the carbon–carbon double bonds (C = C) in a suitable orientation to undergo photoreaction between neighboring complexes.

Synthesis and Characterization of GdO<sup>+</sup> Nanosheets Doped with Tm

Tm doped GdOBr compounds were successfully synthesized through solid-state method. Then bromide ion in the as-synthesized compounds Gd0.97Tm0.03OBr was exchanged by P-toluene sulfonate ion in P-toluene sulfonate sodium solution. A sol-solution was obtained after the ultrasound treatment of intercalating sample in formamide solution. In addition, many rare-earth metal elements can launch visible light when excited. The emissions of Tm3+ at 478nm originated from the transition of Tm3+(1G4→3H6) was observed.

Crystal structure and thermal decomposition mechanism of a 5-aminotetrazole copper(II) complex

A novel 5-aminotetrazole mixed ligands complex of formula [Cu(PTS)2(ATZ)2(H2O)2] (C16H24CuN10O8S2, PTS = p-toluenesulfonate, ATZ = 5-aminotetrazole) has been obtained by the reaction of 5-aminotetrazole with copper acetate and p-toluenesulfonic acid on heating in water. It was characterized by elemental analysis, FT-IR spectroscopy, and X-ray single crystal diffraction. The compound crystallizes in monoclinic system, space group P21/c, Z = 2, a = 14.079(4) A, b = 6.088(3) A, c = 14.632(4) A, β = 105.268(4)°, V = 1209.8(5) A3. The central copper(II) cation is coordinated by two N atoms and four O atoms from two ATZ ligands, two water molecules and two p-toluenesulfonate ions to form a six-coordinated and distorted octahedral structure. Neutral ATZ is coordinated in the monodentate mode by the N(4) atom. The sulfonate group of the PTS ligand remains weak-coordinated modes and forms a number of hydrogen bonds with water molecule ligands and ATZ ligands. A supramolecular framework is connected by electrostatic interaction, weak coordinated bonding, hydrogen-bonding, and π–π interaction. The thermal decomposition mechanism of the title compound was predicted based on DSC, TG-DTG, and FT-IR analyses. Thermolysis of ATZ and its several derivatives is compared.

Quantum chemical study of p-toluenesulfonic acid, p-toluenesulfonate anion and the water–p-toluenesulfonic acid complex. Comparison with experimental spectroscopic data

The 1:1 p-toluenesulfonic acid–water complex, p-toluenesulfonic acid itself and the p-toluenesulfonate anion were studied at HF and B3LYP/6-31+G(d,p) levels of theory. Full geometry optimizations of the aforementioned species reveal non-existence of ionic minima on the explored 1:1 p-toluenesulfonic acid–water complex potential-energy hypersurfaces (PEHSs), implying that two or three p-toluenesulfonate ions (+crystal field) are required to stabilize the ionic H 3O +⋯C 6H 4(CH 3)SO 3 − species found in the crystal structure of p-toluenesulfonic acid monohydrate (in fact, oxonium p-toluenesulfonate). Harmonic vibrational analyses of the p-toluenesulfonic acid–water complex as well as of the p-toluenesulfonate anion were used to confirm some of our previous reassignments of bands in the vibrational spectra of p-toluenesulfonic acid monohydrate and several metal p-toluenesulfonates. According to the quantum chemical results, the symmetric SO 3 bending mode should appear at higher frequencies than the antisymmetric one. A more consistent interpretation of the region of appearance of the SO 3 stretching modes is proposed which is in excellent agreement with the experimental spectroscopic data. The frequency of the multireference benzenoid ν 14 (B 2u) mode (the “Kekulé” type vibration) is excellently predicted at the B3LYP level of theory, while the HF methodology performs significantly poorer in this respect. The interaction energies as well as the vibrational frequency shifts of the most relevant modes are also presented for the 1:1 p-toluenesulfonic acid–water complex. The NBO analysis is employed to analyze the charge transfer interaction within the complex.

Roles of Anion and Solvent in the Self-Assembly of Silver(I) Complexes Containing 2,3-Diphenylquinoxaline

A series of Ag(I) complexes with zero-, one- and two-dimensional structures have been successfully prepared by the reactions of 2,3-diphenylquinoxaline, L, with corresponding Ag(I) salts in various solvents, which were characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Complexes of the type [Ag(L)2](X) (X = ClO4, 1; X = PF6, 2; and X = SbF6, 3) are monomeric, while the complexes {[Ag(L)(L′)][X]}∞ (X = BF4, L′ = H2O, 4; X = BF4, L′ = CH3CN, 5; and X = ClO4, L′ = CH3CN, 6), [Ag(L)(CF3SO3)·0.5CH3OH·H2O]∞, 7·0.5CH3OH·H2O, and {[Ag(L)][SbF6]·0.5CH2Cl2}∞, 8·0.5CH2Cl2, show 1-D polymeric infinite chains. The ClO4− anions in complex 6 interact with the rings in a tridentate bonding mode forming the rare [ClO4-π]n zigzag chain. The molecules of the complex Ag2(L)(NO3)2(DMF)2, 9, are dinuclear, while complexes of the type [Ag2(L)(NO3)2(L′)2]∞ (L′ = H2O, 10, and L′ = CH3CN, 11) show 1-D ladderlike chain structures, and the [Ag2(L)]2+ units are interlinked by H2O molecules and/or NO3− anions. The complexes [Ag2(L)(NO3)2]∞, 12, and [Ag(L)(p-TsO)]∞ (p-TsO = p-toluenesulfonate), 13, show 2-D distorted hexagonal net and 2-D pleated rectangular grids, respectively. For complexes 1−8 with noncoordinating anions, those with coordinated or packed solvent molecules show the polymeric structures, whereas those without solvent molecule are mononuclear. For complexes 9−13, the nitrate and p-toluenesulfonate ions are found to be coordinating and the bonding modes of nitrate anions are dependent on the nature of the solvents. All the complexes exhibit emissions which may be tentatively assigned as intraligand (IL) π → π* transitions.

Thermodynamic Characteristics of Uranyl Benzenesulfonate and p-Toluenesulfonate

The enthalpies of solution of anhydrous and hydrated uranyl benzenesulfonate (I) and p-toluenesulfonate II) in 4 M HCl were determined. The standard enthalpies of formation of I and II and their crystal hydrates from uranium trioxide, sulfonic acids, and water and enthalpies of water addition to anhydrous salts and lower hydrates of II were calculated. The enthalpy of addition of water molecule to II·H2O is about half that of addition to II·3H2O. With regard to all approximations in calculations, the enthalpy of formation of II from amorphous uranium trioxide and aqueous solution of the corresponding acid is by approximately 20 kJ mol-1 more negative as compared to I. It was concluded that the electron-donor power of the p-toluenesulfonate ion is noticeably greater than that of the benzenesulfonate ion, which determines the difference in the properties of II and I.

Structural characterization of protonated benzeneseleninic acid, the dihydroxyselenonium ion

The structure of the dihydroxyphenylselenonium ion (C(6)H(7)O(2)Se(+)) has been determined in its benzenesulfonate (C(6)H(5)O(3)Se(-)-) and p-toluenesulfonate (C(7)H(7)O(3)S(-)) salts. Whereas the former salt is disordered, the latter less dense salt is well defined. This difference in crystallization behaviour is attributed to a C-H.O hydrogen bond involving the methyl group of the p-toluenesulfonate ion. The two salts display very similar hydrogen-bond arrangements and differ only with respect to the stacking of the phenyl groups. The dihydroxyselenonium ion is a strong acid with a pK value of -0.9 determined from the variation of the (77)Se chemical shift. A comparison with the two deprotonated species reveals a systematic increase in the Se-O bond lengths and the pyramidal configuration around Se with the number of protons attached.

Behavior of Model Ionic Compounds under Thermospray Liquid/Liquid Extraction Conditions

Our previously reported procedure for the extraction of semivolatile and nonvolatile organic compounds from aqueous samples by thermospray liquid/liquid extraction was extended to the extraction of charged organic compounds from water. By thermally disrupting or extricating the solvation shell of hydrated ions, the thermospray process facilitates the extraction of these analytes from the aqueous matrix. The effects of probe temperature, probe flow rate, and sample pH on the extraction efficiency of model compounds such as phenylalanine, benzoate ion, p-toluenesulfonate ion, and naphthalenetrisulfonic acid trisodium salt were investigated. Under optimized conditions, the percent recoveries for these compounds were 95, 97, 91, and 13%, respectively.

Electrochemically synthesized polypyrrole films: effects of polymerization potential and electrolyte type

Polypyrrole films containing either the perchlorate or p-toluenesulfonate ion were prepared from an aqueous solution by applying an anodic potential in the range 0.6–2.0 V (relative to a saturated calomel electrode). The effects of applied potential on electropolymerization, morphology, chemical structure, electrochemical properties and tensile modulus have been investigated. The chronoamperometric response of pyrrole electropolymerization depends on the applied potential and not on the counterion. The electrochemical properties and structure of polypyrrole depend on the polymerization potential as well as the counterion. An empirical expression relating peak current to the scan rate and charge passed during polymerization is proposed. This relationship provides some insight into the nature of the polypyrrole switching reaction. For polypyrrole containing perchlorate, the concentration of dicationic species or dipolarons decreases as the polymerization potential increases from 0.6 to 1.0 V. The large concentration of dicationic species in polypyrrole prepared at 0.6 and 0.75 V is responsible for the second reduction peak observed in the cyclic voltammograms.

ChemInform Abstract: Solvent Effects on the Interionic Structure of Ion Pairs. Electric Dipole Moments and IR Spectra of N‐Allyl‐N‐ethyl‐N‐methylanilinium p‐Toluenesulfonate Ion Pairs in a Series of Solvents

ChemInformVolume 21, Issue 41 Physical Organic Chemistry ChemInform Abstract: Solvent Effects on the Interionic Structure of Ion Pairs. Electric Dipole Moments and IR Spectra of N-Allyl-N-ethyl-N-methylanilinium p-Toluenesulfonate Ion Pairs in a Series of Solvents M. K. BEGUM, M. K. BEGUM Chem. Dep., Brandeis Univ., Waltham, MA 02254, USASearch for more papers by this authorE. GRUNWALD, E. GRUNWALD Chem. Dep., Brandeis Univ., Waltham, MA 02254, USASearch for more papers by this author M. K. BEGUM, M. K. BEGUM Chem. Dep., Brandeis Univ., Waltham, MA 02254, USASearch for more papers by this authorE. GRUNWALD, E. GRUNWALD Chem. Dep., Brandeis Univ., Waltham, MA 02254, USASearch for more papers by this author First published: October 9, 1990 https://doi.org/10.1002/chin.199041039Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume21, Issue41October 9, 1990 RelatedInformation

Solvent effects on the interionic structure of ion pairs. Electric dipole moments and infrared spectra of N-allyl-N-ethyl-N-methylanilinium p-toluenesulfonate ion pairs in a series of solvents

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSolvent effects on the interionic structure of ion pairs. Electric dipole moments and infrared spectra of N-allyl-N-ethyl-N-methylanilinium p-toluenesulfonate ion pairs in a series of solventsM. Kohinoor Begum and Ernest GrunwaldCite this: J. Am. Chem. Soc. 1990, 112, 13, 5104–5110Publication Date (Print):June 1, 1990Publication History Published online1 May 2002Published inissue 1 June 1990https://doi.org/10.1021/ja00169a018RIGHTS & PERMISSIONSArticle Views91Altmetric-Citations9LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (912 KB) Get e-Alerts Get e-Alerts

Electrically Conductive Polymer Composite from Polypyrrole and Electrodeposited Poly(p-phenylene terephthalamide) Film

Electrically conductive composites from polypyrrole (PPy) and poly(p-phenylene terephthalamide) (PPTA) were formed by electropolymerization of pyrrole on the electrode covered with PPTA film prepared by electrolysis of PPTA polyanions dissolved in dimethylsulfoxide. For the PPTA film annealed above 250°C, the polymerization of pyrrole hardly took place. Based on DSC measurements, it was found that the remaining solvent of PPTA film was closely related to composite formation. The morphologies of the composites varied, depending on the supporting electrolytes of tetraethylammonium p-toluenesulfonate and lithium perchlorate. The conductivity of the composite was 5–50 S cm−1. The composite showed improved mechanical properties: tensile strength was 142 MPa and tensile modulus was 6.2 GPa for the PPy(TsO−)/PPTA composite, where TsO− denotes the p-toluenesulfonate ion. The temperature dependence of the dynamic viscoelasticity of the PPy(TsO−)/PPTA composite was well explained by Takayanagi’s two-phase model, which was also consistent with SEM observation. The conductivities of the composites doped with p-toluenesulfonate and perchlorate were both retained at all times up to 150°C, whereas that of the pure PPy film decreased to 80% the original value after annealing at 150°C, being independent of the dopants. PPTA film was dimensionally stable and heat-resistant, and these properties provided a stable conductive composite film.

ChemInform Abstract: NORMAL VIBRATIONS OF BENZENESULFONATE AND BENZENE‐D5‐SULFONATE IONS

Infrared and Raman spectra of sodium benzenesulfonate and its fully C-deuterated derivative have been recorded in the solid state and in the aqueous solution. The normal coordinate analysis has been made for C6H5SO3− and C6D5SO3− ions based on the C2V symmetry. A valence force field was assumed and the force constants were refined by the least squares method. It was found that the diagonal force constants for the CH out-of-plane bending vibrations at the ortho and the para positions are greater than the corresponding constant for the meta position. This result reflects well the effect of the electron attractive substituent in monosubstituted benzene derivatives. The force constants obtained were transferred to p-toluenesulfonate ion successfully.

Normal Vibrations of Benzenesulfonate and Benzene-d5-sulfonate Ions

Abstract Infrared and Raman spectra of sodium benzenesulfonate and its fully C-deuterated derivative have been recorded in the solid state and in the aqueous solution. The normal coordinate analysis has been made for C6H5SO3− and C6D5SO3− ions based on the C2V symmetry. A valence force field was assumed and the force constants were refined by the least squares method. It was found that the diagonal force constants for the CH out-of-plane bending vibrations at the ortho and the para positions are greater than the corresponding constant for the meta position. This result reflects well the effect of the electron attractive substituent in monosubstituted benzene derivatives. The force constants obtained were transferred to p-toluenesulfonate ion successfully.