17O and 33S nuclear magnetic shielding of sulfur trioxides from the experimental measurements and theoretical calculations

In a recent ¹⁷O NMR spectra of liquid sulfur trioxide, several unexpected peaks appeared with the temperature‐dependent integrated peak ratio. In order to interpret NMR spectra and assign peaks to possible molecular structures, the theoretical quantum mechanical density functional theory and Møller–Plesset second‐order perturbation theory calculations were performed. It is suggested that in the liquid sulfur trioxide, apart from monomeric SO₃, a significant amount of (SO₃)₃ cyclic trimers should appear. No theoretical data support hypothesis on (SO₃)₂ dimers formation. Copyright © 2014 John Wiley & Sons, Ltd.     

A new type of cation‐exchange polymeric microspheres with pendant methylenethiol groups

Synthesis and characterization of the new styrene microspheres with pendant methylenethiol groups are presented. At the first stage, the polymeric matrices were obtained by the suspension–emulsion polymerization of monomers: styrene (St) with 2,3‐(2‐hydroxy‐3‐methacryloyloxypropoxy)naphthalene (NAF.DM) or (bis[4(2‐hydroxy‐3‐methacryloyloxypropoxy)phenyl]sulfide (BES.DM) or divinylbenzene (DVB). At the second stage, the modification of the sythesized matrices was performed as follows: the matrices were reacted with paraformaldehyde in the presence of hydrochloric acid forming chloromethyl derivatives. Next, by reaction with thiourea, a thiouronium salt was obtained, and then the hydrolysis with NaOH solution and acidification with HCl were carried out. Finally, microspheres with –CH₂SH groups on their surface were obtained. The –SH group content (elemental analysis), thermal properties (thermogravimetric analysis), Fourier transform infrared as well as the swelling characteristics of the functional microspheres were examined. The surface texture was also visualized by the atomic force microscopy (AFM) method. The obtained polymers were screened towards sorption of Cu(II) ions. It was found that a better correlation between the experimental Cu(II) uptake and the theoretical curves predicted by the Langmuir or Freundlich models is obtained in the case of the DVB–St–SH polymer. In the case of the BES.DM–St–SH and 2,3‐NAF–St–SH ones, the Freundlich model corresponded quite well to the experimental data. Copyright © 2013 John Wiley & Sons, Ltd.     

The influence of oxidation number of sulfur on the polymerization and thermo-mechanical properties of dimethacrylate copolymers

Structure and characterization of the sulfur-containing monomers bis[4(2-hydroxy-3-methacryloyloxypropoxy)phenyl]sulfide (S·DM), bis[4(2-hydroxy-3-methacryloyloxypropoxy)phenyl]sulfinyl (SO·DM), bis[4(2-hydroxy-3-methacryloyloxypropoxy)phenyl]sulfonyl (SO₂·DM), and their photopolymerization with N-vinyl-2-pyrrolidone (NVP) are presented. The monomers were obtained in the reaction of derivatives of aromatic diols with 2-(chloromethyl)oxirane in the two-phase liquid/liquid system, including organic and aqueous phases. Next, esterification of the obtained diglycidyl ether was carried out with the use of methacrylic acid. Photopolymerization of the compositions (S·DM, SO·DM, SO₂·DM and NVP) and the initiator (Irgacure 651) was carried out. The influence of oxidation number of sulfur on the properties of the obtained copolymers was studied. The following properties were determined: density, glass transition temperature, Young’s modulus, hardness and tensile strength. Additionally, dynamic-mechanical and thermal properties were investigated. Thermal properties of copolymers under different conditions (in air, in nitrogen and in helium) were tested.     

Performance of density functional theory in computing nonresonant vibrational (hyper)polarizabilities

A set of exchange‐correlation functionals, including BLYP, PBE0, B3LYP, BHandHLYP, CAM‐B3LYP, LC‐BLYP, and HSE, has been used to determine static and dynamic nonresonant (nuclear relaxation) vibrational (hyper)polarizabilities for a series of all‐trans polymethineimine (PMI) oligomers containing up to eight monomer units. These functionals are assessed against reference values obtained using the Møller–Plesset second‐order perturbation theory (MP2) and CCSD methods. For the smallest oligomer, CCSD(T) calculations confirm the choice of MP2 and CCSD as appropriate for assessing the density functionals. By and large, CAM‐B3LYP is the most successful, because it is best for the nuclear relaxation contribution to the static linear polarizability, intensity‐dependent refractive index second hyperpolarizability, static second hyperpolarizability, and is close to the best for the electro‐optical Pockels effect first hyperpolarizability. However, none of the functionals perform satisfactorily for all the vibrational (hyper)polarizabilities studied. In fact, in the case of electric field‐induced second harmonic generation all of them, as well as the Hartree–Fock approximation, yield the wrong sign. We have also found that the Pople 6–31+G(d) basis set is unreliable for computing nuclear relaxation (hyper)polarizabilities of PMI oligomers due to the spurious prediction of a nonplanar equilibrium geometry. © 2013 Wiley Periodicals, Inc.     

New basis sets for the evaluation of interaction‐induced electric properties in hydrogen‐bonded complexes

Interaction‐induced static electric properties, that is, dipole moment, polarizability, and first hyperpolarizability, of the CO? (HF)_n and N₂? (HF)_n, n = 1–9 hydrogen‐bonded complexes are evaluated within the finite field approach using the Hartree–Fock, density functional theory, Møller–Plesset second‐order perturbation theory, and coupled cluster methods, and the LPol‐n (n = ds, dl, fs, fl) basis sets. To compare the performance of the different methods with respect to the increase of the complex size, we consider as model systems linear chains of the complexes. We analyze the results in terms of the many‐body and cooperative effects. © 2012 Wiley Periodicals, Inc.     

Detailed study of a two component smectic 4TPB–8OCB system with a nematic gap. Phase diagram and viscosity study

Abstract

The phase diagram of a two component system composed of two smectic compounds: 4-octyloxy-4′-cyanobiphenyl (8OCB) and 4-isothiocyanatophenyl 4-butylbenzoate (4TPB) was investigated. Three Miesowicz viscosity coefficients η₁, η₂, η₃ and the refractive indices at different temperatures as well as the enthalpies of the phase transitions were measured. It was stated, that the properties of the induced nematic phase, for example, the nematic phase existing between two smectic regions, are the same as the ones observed in the case of low viscosity nematic mesogens.     

A convenient synthesis and the mesomorphic properties of new chiral ferroelectric thiobenzoates

A secondary chiral (R)-(?)-2-alcohol underwent the Mitsunobu reaction with triphenylphosphine, diethyl azodicarboxylate and ethyl 4-hydroxybiphenylcarboxylate, resulting in the desired (S)-(+)-product with high enantiomeric purity (>99% ee), with the chiral branched chain attached to the biphenyl. This method is operationally simple and provides the very important chiral precursor in good yields (62% in dry THF and 72% in dry Et₂O). The condensation of the (S)-(+)-acid chloride from this material and a suitable 4-n-alkylthiophenol in toluene in the presence of pyridine or triethylamine furnishes the chiral (S)-(+)-thiobenzoate liquid crystals in good yields (80–83% in pyridine and 65–68% in Et₃N). (S)-(+)-4-(1-Methylheptyloxy)biphenyl 4-alkylthiobenzoates are abbreviated (S)-MHOBSn , where n varies from 4 to 10 and denotes the number of carbon atoms in the alkyl chain. DSC, polarizing microscopy and X-ray diffraction showed that the (S)-MHOBSn series possesses a rich phase polymorphism: two highly ordered tilted phases CrG* and SmI*, as well as the ferroelectric smectic C (SmC*) and chiral nematic (N*) phase. In this series, the seldom observed transition between the chiral phases SmI*–SmC* is seen. All the compounds possess stable enantiotropic SmC* and N* phases. The existence of weak intermolecular hydrogen-bonding in (S)-MHOBSn was confirmed by FTIR spectroscopy.