Phase-transfer catalysis in reactions with the participation of polyvinyl chloride

When polyvinyl chloride is dehydrochlorinated under conditions of phase transfer catalysis, the nature of the interface determines the supramolecular structure of the synthesized polyacetylene, the packing density of crystalline regions in the polyacetylene, and the chemical properties of the polymer. The ionic mechanism of catalysis of these reactions has been established.This review is based on materials reported at the Conference Phase-Transfer Catalysis: New Ideas and Methods(March, 1994).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1886–1894, October, 1995.     

EPR in strongly irradiated polyacetylene

The influence of -irradiation on the paramagnetic properties of polyacetylene has been studied. The samples were exposed to -irradiation up to a dose of 3 MGy.     

Effect of ancillary ligands on the properties of heteroleptic green iridium dendrimers functionalized with carbazole dendrons

A series of heteroleptic green iridium dendrimers functionalized with carbazole dendrons, such as G2(pic) and G2(acac), have been synthesized, in which picolinic acid and acetylacetone are used as the ancillary ligands, respectively. Compared with the corresponding homoleptic iridium dendrimer G2 (8%), these heteroleptic ones can be prepared under mild conditions with total yields as high as 55-67%. Both the dendrimer G2(pic) and G2(acac) display bright green emissions with photoluminescence quantum yields higher than 0.80 in toluene solution. As a result, a maximum external quantum efficiency of 7.1% (21.0 cd/A) for G2(pic) and 7.7% (25.8 cd/A) for G2(acac) has been realized based on non-doped device configuration. The state-of-art performance indicates that the heteroleptic dendrimers can be promising candidates used for non-doped electrophosphorescent devices, especially when the ease of synthesis in a large scale is considered.     

Preparation of soluble functional polymers by modification of nanosized polyacetylene

The reaction of electrophilic reagents such as halogens, nitric and sulfuric acids, and sulfur dioxide with nanosized stereoregular polyacetylene was studied. Polymers with chlorine content as much as 65% were obtained and the MW properties of the polymers were found to depend on the structure of pristine polyacetylene prepared under various conditions. The reaction between nitric acid and stereoregular polyacetylene occurred to give first [CH(NO₂)CHCHCH(OH)]_n while the totally nitrated product [CH(NO₂)CH(ONO₂)]_n was obtained with nitrogen content of 18.3% after complete nitration. GPC, NMR- and IR-spectroscopy were used for structural and MWD analysis of the original polyacetylene and obtained products. The mechanism of the reaction between electrophilic reagents and polyacetylene is discussed on the basis of the experimental and literature data.     

Chiral Poly(4‐ethynylbenzoyl‐L‐valine)‐Induced Helical Self‐Assembly of Alkynylplatinum(II) Terpyridyl Complexes with Tunable Electronic Absorption,Emission, and Circular Dichroism Changes

The aggregation and self‐assembly of square‐planar alkynylplatinum(II) complexes is induced by the use of a chiral polyacetylene with a helical conformation (see scheme). The chain helicity of the chiral polyacetylene under basic conditions has also been demonstrated to be enhanced by the presence of the positively charged platinum(II) complexes.

     

A New Disubstituted Polyacetylene for the Detection of α‐Amino Acids

New imidazole‐functionalized disubstituted polyacetylene was synthesized by utilizing the postfunctional strategy. In addition, its ability to sense copper ions and α‐amino acids by fluorescence quenching has been studied. The quenching of the fluorescence of the imidazole‐functionalized disubstituted polyacetylene was observed at a very low level of Cu²⁺ (7.0 × 10⁻⁷ mol · L⁻¹). The fluorescent intensity decreased rapidly upon the increase of the concentration of the added solution of Cu²⁺. It was expected that the addition of α‐amino acids to the solution of the polyacetylene/Cu²⁺ complex could turn on the fluorescence of the polyacetylene, if α‐amino acids could remove the copper ions from the complex. Glycine, was used for testing: upon the addition of glycine the quenched fluorescence of P1 turned on immediately. The detection limit was as low as 6.0 × 10⁻⁵ mol · L⁻¹.

     

Thermal- and UV-induced cis/trans isomerization of undoped polyacetylene films. An ESR and IR investigation

The UV- and thermal-induced cis→trans isomerization of undoped polyacetylene (PA) films has been investigated. The results have shown that temperature and UV light promote the isomerization of PA with a similar mechanism. We suggest that the formation of paramagnetic defects in trans PA takes place by bond rehybridization, in agreement with previous hypotheses, and that both spin concentration and spin delocalization depend on the temperature of isomerization. It was found that under UV irradiation thermal cis→trans isomerization of polyacetylene also takes place at temperatures at which the sole thermal treatment isomerization is much lower or nil, and we suggest that the possibility of preparing trans PA under relatively mild conditions may lead to a better material.     

Molecular and spectroscopic properties of a polarizer based on a block copolymer of vinylalcohol and acetylene

The preparation of a high efficiency polarizer derived from the block copolymer, poly(vinylalcohol‐b‐acetylene) will be described. The orientations of the polyacetylene chromophore and the polyvinylalcohol matrix have been analyzed by polarized UV/Vis and FTIR spectroscopy, respectively. For moderately stretched films (L/Lo = 3.0‐7.0), the degree of orientation for the polyacetylene segments greatly exceeds that predicted from a simple, pseudoaffine deformation model. For the visible spectral region, dichroic ratios in the range of 60 to 100 are easily achieved, thus permitting films of this polymer to function as a high efficiency, polarizing optical element. Data from a series of sample tilting experiments utilizing polarized UV/Vis radiation are consistent with the polyacetylene segments being distributed uniaxially about the stretching direction. However, analogous experiments in the infrared indicate that the PVA matrix has significant biaxial character. Other novel characteristics of this polarizer will be discussed, such as its thermal and chemical stability.     

Ultrafast Deactivation Mechanism of the Excited Singlet in the Light‐Induced Spin Crossover of [Fe(2,2′‐bipyridine)3]2+

The mechanism of the light‐induced spin crossover of the [Fe(bpy)₃]²⁺ complex (bpy=2,2′‐bipyridine) has been studied by combining accurate electronic‐structure calculations and time‐dependent approaches to calculate intersystem‐crossing rates. We investigate how the initially excited metal‐to‐ligand charge transfer (MLCT) singlet state deactivates to the final metastable high‐spin state. Although ultrafast X‐ray free‐electron spectroscopy has established that the total timescale of this process is on the order of a few tenths of a picosecond, the details of the mechanisms still remain unclear. We determine all the intermediate electronic states along the pathway from low spin to high spin and give estimates for the deactivation times of the different stages. The calculations result in a total deactivation time on the same order of magnitude as the experimentally determined rate and indicate that the complex can reach the final high‐spin state by means of different deactivation channels. The optically populated excited singlet state rapidly decays to a triplet state with an Fe d⁶(${{\rm t}{{5\hfill \atop {\rm 2g}\hfill}}}$ ${{\rm e}{{1\hfill \atop {\rm g}\hfill}}}$ ) configuration either directly or by means of a triplet MLCT state. This triplet ligand‐field state could in principle decay directly to the final quintet state, but a much faster channel is provided by internal conversion to a lower‐lying triplet state and subsequent intersystem crossing to the high‐spin state. The deactivation rate to the low‐spin ground state is much smaller, which is in line with the large quantum yield reported for the process.     

Synthesis and characterization of polylactide functionalized polyacetylenes

The paper deals with the synthesis and polymerization of novel poly(l-lactide)-derived acetylene monomers and the analysis of the thermal properties of the formed graft copolymers. Poly(l-lactide) macromonomers with different acetylene end groups were prepared using stannous octanoate as a catalyst in the presence of various hydroxyacetylenes. Next, the well-characterized macromonomers were subjected to polymerization using [{RhCl(nbd)}₂]/Et₃N and [RuCl₂(CH–o–OiPrC₆H₄)(IMesH₂)] to obtain graft copolymers. Investigation of these graft copolymers by GPC and NMR spectroscopy revealed the presence of some poly(l-lactide) formed as a side product during the ring opening polymerization of l-lactide. The thermal stability of the polymeric materials has been studied as a function of the polyacetylene backbone substituents and the length of poly(l-lactide) side chains. Introducing polyacetylene into polyester increased the polymer stability. The thermal degradation behavior of the synthesized materials depends on the length of poly(l-lactide) chains and also on l-lactide homopolymer impurities in the graft copolymers.     

XPS Studies of PtCl4 and H2PtCl6·6H20 doped polyacetylene

The PtCl₄ and H₂PtCl₆-6H₂O doped polyacetylene were studied by X-ray photoelection spectroscopy and transmission electron microscopy. We found that both Pt 4f and Cl 2p peaks could be resolved into two components both with a splitting of ca. 1.5 eV. The higher binding energy components of Pt 4f peak is attributed to Pt⁴⁺ and the lower binding energy one to Pt²⁺ species. From quantitative analysis of the results of decomposition of both Pt 4f and Cl 2p peaks it was found that an atomic ratio of chlorine to platinum for Pt²⁺ species is (Cl) / (Pt) = 2 and that for Pt⁴⁺ species is (Cl) / (Pt) = 6 for both PtCl₄ and H₂PtCl₆·6H₂O doped polyacetylene. The C 1s peaks could be decomposed into two components separated by ca. 1 eV. The intensity of the higher binding energy component increased with increasing dopant concentration. These indicate that the platinum salt doping proceeds through charge transfer from polyacetylene chain to platinum atom resulting in a partial reduction from Pt⁴⁺ to Pt²⁺ state. The existence of PtCl₂ cluster on the surface of the doped polyacetylene film was supported by transmission electron microscopy and electron diffraction observations. These results indicate that a random distribution of the dopant along the macromolecular chain, and the charge per carbon atom in the metallic region of doped polyacetylene has been estimated to be 0.2 |e|. From these results the mechanism of the PtCl₃ and H₂PtCl₆·6H₂O doping process in polyacetylene is clarified as follows: Thus the dopant anion in polyacetylene is PtCl,^2? for both PtCl₄ and H₂PtCl₆·6H₂O doping.     

Gamma radiolysis of a heavy petroleum fraction

A relatively heavy petroleum fraction called distillate aromatic extract (DAE) which has been proposed to be the carrier of the emission bands of certain astronomical objects like protoplanetary nebulae (PPNe) and the so-called unidentified infrared bands (UIBs), has been radiolyzed with -radiation to a total dose of 1 MGy. The stability of DAE toward radiation was assessed by FT-IR and electronic spectroscopy. The gases produced during radiolysis have been identified by GC. They were essentially H₂ and CH₄. A certain degree of crosslinking has been verified on the radiation-processed material by measuring the hexane insoluble fraction of DAE, which increased dramatically after the radiation treatment. Further analyses were conducted using high performance liquid chromatography (HPLC) on the radiation processed sample in comparison to the pristine sample.     

Isotropic paramagnetic shifts of the phosphorus and proton magnetic resonance and the spin density distribution in paramagnetic complexes of triphenylphosphine with nickel acetylacetonate

The Isotropic paramagnetic shifts in the H¹ and P³¹ NMR spectra of triphenylphosphine, forming labile complexes in chloroform with the acetylacetonato compound of nickel(II), have been measured. The concentration dependence of the shifts has been used to calculate the hyperfine interaction constants and the spin densities in an individual complex, on the assumption that the complex has the composition [Ni(AA)₂] (PPh₃)₂. It has been found that the spin density in the sp³ hybrid orbital of the phosphorus atom is positive and amounts to not less than 10%, indicating a -mechanism of transfer of spin density from the nickel to the phosphorus. The spin densities on the carbon atoms of the phenyl rings are smaller fay about two orders of magnitude than those on the phosphorus atom, and this is attributed to the orientation of these rings, which is unsuitable for conjugation with the unshared pair. The contributions of the different mechanisms to the delocalization of the spin density from the phosphorus atom to the -system of the rings have been estimated.The authors wish to express their gratitude to the late Academician V. V. Voevodskii, whose initiative and constant support made this joint work possible. The authors thank A. Nesmei, for assistance in the construction of the phosphorus resonance measurement apparatus, and G. M. Zhidomirov, for discussion of the results.     

Low-spin excitations of quasi-one-dimensional polyacetylene chains in Hartree-Fock models

In the -electron approximation taking into account Coulomb repulsion and electron correlation, we have calculated the excitation energy _s of the state with spin s=1, 2, 3 in long polyacetylene chains. From numerical calculations, we have established the dependence _s=(2s–1)₁, which is satisfactorily satisfied for the different wave functions used (from the unrestricted and two variants of the extended Hartree-Fock method). For some of the solutions, localization of the excitation in 2s–1 fragments of the chain is characteristic, which indicates the possibility of interpreting it in terms of a soliton.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 6, pp. 716–719, November–December, 1990.     

Photolysis of dialkyl metallocenes of the titanium group; an ESR study

Photolysis in the visible and the UV region of dialkyl metallocenes of the titanium group is studied by ESR. The primary process is shown to be homolytic cleavage of the metal—alkyl bond, with formation of paramagnetic metal species and organic free radicals. The first were identified from the ESR signal produced and the second from the spectra of their spin adducts with the appropriate spin trap. The MC bond cleavage depends on the metal and on the radiation wavelength.     

Effect of transition metal doping and carbon doping on thermoelectric properties of YB66 single crystals

We have been investigating the high-temperature thermoelectric properties of some novel rare earth borides with a structure containing B₁₂ icosahedra. Doping effects on the TE properties in such systems were investigated for the first time. A series of Nb-doped YB₆₆ and C-doped YB₆₆ single crystals were grown by the floating zone method. The Nb-doped compounds have approximate chemical formulas ranging from YNb_0.30B₆₆ to YNb_0.33B₆₆ while the C-doped compound has a formula of YB₆₆C_0.6. The effect of Nb-doping on the thermoelectric properties was not monotonic and appears to be complex. As a result of Nb-doping, the room temperature resistivity and the characteristic temperature T₀ were considerably reduced. At room temperature the power factor of the Nb-doped YB₆₆ sample with 89% site occupancy was three times greater than that of non-doped YB₆₆. However, in the important high-temperature region, the non-doped sample actually exhibited the highest power factor for . Furthermore, owing to a structural feature of YB₆₆, thermal conductivity actually increases with doping of transition metals. Taking into account all the thermoelectric properties, transition metal doping of YB₆₆ is therefore not suitable for our purposes. On the other hand, doping of carbon, which is assumed not to go into the same sites as the transition metals, yielded a lowering of the thermal conductivity. Furthermore, contrary to Nb-doping, carbon doping did not result in a reversal of the relative magnitude of resistivity at extremely high temperatures and therefore, an increase in the figure of merit of factor 2 was realized at 1000 K.     

A Spin‐Crossover Cluster of Iron(II) Exhibiting a Mixed‐Spin Structure and Synergy between Spin Transition and Magnetic Interaction

How low can you go? An Fe^II₄ square was prepared by self‐assembly and exhibits both thermally induced and photoinduced spin crossover from a system with four high‐spin (HS) centers to one with two high‐spin and two low‐spin (LS) centers. The spin‐crossover sites are located on the same side of the square, and the spin transition and magnetic interactions (see picture) are synergistically coupled.

     

A quantum chemical study of interchain hopping model of negatively charged solitons in polyacetylene

Phonon-assisted interchain hopping of negatively charged solitons in polyacetylene has been studied using a local chemical reaction model CH + CH₄ → CH₄ + CH. Quantum chemical characteristics of the electron transfer process have been analyzed in terms of the dynamic electron density and the mutual polarization moment. The CH stretching vibrational motion of CH₄, which is a local model of the sp³ defect, has been found to play a significant role for the electron transfer. The excitation of the corresponding vibrational mode of the sp³ defect would promote the interchain hopping of the charged soliton. The electron transfer process has also been studied in terms of the “regional” density functional theory. It has been shown that the driving force of the electron transfer is represented by the regional chemical potentials.     

Isomer ratios of86,87Y and84Rb in the alpha induced reaction on85Rb

Isomer ratios for⁸⁷Y,⁸⁶Y and⁸⁴Rb from -induced reactions on⁸⁵Rb in the energy range between 20 and 60 MeV have been measured. The data show a characteristic increase followed by a decrease with the increase in bombarding energy. The fall in the isomer ratio values are explained on the basis of enhanced angular momentum depletion by the precompound particles and thereby leaving the compound system at low angular momentum states. A different reaction mechanism has been proposed for the low yield of the high spin isomer in the /, n/ reaction in⁸⁵Rb.     

Radiation resistance of pyridine type anion exchange resins for spent fuel treatment

The resistance against radiation of the tertiary pyridine resins synthesized for the treatment of spent nuclear fuels and high level radioactive waste was evaluated. After irradiation at 10 MGy, only approximately 10% or less of the exchange groups were lost in HCl solutions regardless of their concentrations, while 3040% were lost in HNO₃. The pyridine resin has shown remarkable resistance against radiation particularly in HCl solution. It has been revealed that the decomposition of pyridine type resins results from the scission of the principal chains. An irradiation study was conducted also on the quaternary ammonium resins. Quatemization ratio was found to be reduced in HNO₃ solutions at 10 MGy irradiation.