A theoretical study of the [4 + 4] dimerization of thioformylketene

[reaction and structure: see text] A theoretical study (B3LYP and G3MP2B3) of the dimerization of thioformylketene (1) was performed. Four pathways-two [4 + 2] pathways with thioformylketene (1), one [4 + 4] pathway with 1, and one [4 + 2] pathway involving 1 and thietone (11)-were considered. Interestingly, the [4 + 4] pathway with 1 had the lowest barrier (3.8 kcal/mol). The geometry of the transition state TS14 is unusual, with the forming bonds in the plane of the ketene. This suggests that the reaction is pseudopericyclic.     

Synthesis,spectral and thermal characterization of Bis(diethylammonium) tetrachloromercurate(II)-An nonlinear optical material

A new semiorganic compound, bis(diethylammonium) tetrachloromercurate(II) was grown by slow evaporation solution growth technique at ambient temperature from its aqueous solution. The crystal system and the cell parameters have been identified from the powder X-ray diffraction pattern. The UV–visible absorption of the compound shows absorption at 246 nm and there is absorption observed in the entire visible region indicates that the compound can be used as a nonlinear optical material. The UV–visible transmittance spectrum of grown crystal shows a lower cut-off wavelength at 275 nm and it was found that the crystal is suitable for optoelectronic applications. Thermal studies were carried out to find out the thermal stability and confirm the stoichiometric ratio of the compound. The thermal anomalies in DSC study indicate the occurrence of first order transition in the compound at low temperatures. The FTIR spectrum of the compound characterizes various functional groups. The various kinds of protons and carbons were assigned through NMR (¹H and ¹³C) spectroscopic techniques. The SHG efficiency of the compound was studied by Kurtz-Perry power technique and observed that it has SHG efficiency 1.5 times greater than that of potassium dihydrogen phosphate (KDP). The dielectric constant and dielectric loss of the compound decreases with increase in frequency.     

Stopped-flow kinetics of tetrazine cycloadditions; experimental and computational studies toward sequential transition states

The Diels-Alder cycloadditions of tetrazines (1) with alkynes (2) are expected to give bicyclic adducts (3). Kinetic measurements of the cycloadditions of 1a and 1b with 2a give DeltaG(++) = 19.2 +/- 1.0 and 11.5 +/- 1.2 kcal/mol, respectively. Stopped-flow UV studies on the reaction of 1b with 2a show an isosbestic point at 428 nm; this places an upper limit of 11.6 +/- 2.6 kcal/mol on DeltaG(++) for loss of N(2) from the putative bicyclic intermediate 3b. Calculations (B3LYP/6-31G(d,p) + ZPVE) of transition structures for the reaction of tetrazinediacid 1d with propynylamine 2c are consistent with the experimental results for the reaction of 1b with 2a. This and several related model systems reveal two interesting features of the calculated energy surfaces. First, there may be no barrier for the loss of nitrogen from structures 3 and thus there may be two sequential transition states. This also extends Berson's correlation of activation energy with reaction energy in pericyclic reactions to significantly lower barriers. Second, for the cycloaddition of 4e and 2c, there is neither an intermediate nor a transition state between TS3e and the final product 6e. It appears that the energy surface "turns a corner" in the vicinity of a structure resembling 5e. This is not a mathematically well-defined point but has chemical consequences in that the overall exothermicity of the reaction from 4e to 6e is not felt in TS3e.     

Synthesis,crystal growth and characterisation of 2-aminomethylpyridinium picrate (2-ampp)-a charge transfer molecular complex and organic nonlinear optical material

Single crystals of 2-aminomethylpyridinium picrate (2-AMPP) were grown by slow evaporation-solution growth technique at room temperature. The cell and structural parameters of the grown crystal were determined by single crystal X-ray diffraction analysis. The characteristic functional groups in the compound were identified from Fourier transform infrared spectroscopy. The transmission and absorption spectra of this crystal show that the lower cut-off wavelength lies at 360 nm. Thermal analysis was performed to study the thermal stability of the grown crystal. The powder second harmonic generation efficiency of the grown crystal measured by Kurtz technique is 2 times efficient than potassium dihydrogen orthophosphate (KDP). Vicker's microhardness test showed that the hardness value increases with increasing the applied load up to 50 g. The dielectric measurements of the compound in the frequency region from 50 Hz to 5 MHz showed that the material has lesser defects and can be used for optical application.     

Mechanistic Study of the Titanocene(III)‐Catalyzed Radical Arylation of Epoxides

An atom‐economical and catalytic arylation of epoxide‐derived radicals is described. The key step of the catalytic system is a sequential electron and proton transfer for the rearomatization of the radical σ‐complex and catalyst regeneration. Kinetic, computational, spectroscopic, and cyclovoltammetric investigations highlight the key issues of the reaction mechanism and catalyst stabilization by collidine hydrochloride. Studies employing radicophiles rule out the participation of cations as reactive intermediates.     

Strategies for controlling the active layer morphologies in OPVs

This review focuses on the recent developments in our understanding of active layer morphologies for organic photovoltaic cells and approaches to obtain active layer morphologies for high power conversion efficiencies. The evolution of active layer morphologies, as studied by high resolution electron microscopy, X-ray and neutron scattering, and dynamic secondary ion mass spectrometry, is covered, along with strategies including the use of small molecule additives, polymer nanowires and polymer nanoparticles to realize active layer morphologies. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Mechanistic study of samarium diiodide-HMPA initiated 5-exo-trig Ketyl-Olefin coupling: the role of HMPA in post-electron transfer steps

The mechanistic importance of HMPA and proton donors (methanol, 2-methyl-2-propanol, and 2,2,2-trifluoroethanol) on SmI2-initiated 5-exo-trig ketyl-olefin cyclizations has been examined using stopped-flow spectrophotometric studies. In the presence of HMPA, the rate order of proton donors was zero and product studies showed that they had no impact on the diastereoselectivity of the reaction. Conversely, reactions were first-order in HMPA, and the additive displayed saturation kinetics at high concentrations. These results were consistent with HMPA being involved in a rate-limiting step before cyclization, where coordination of the intermediate ketyl to the sterically congested Sm(III)HMPA both stabilizes the intermediate and inhibits cyclization. Liberation of the contact ion pair through displacement by an equivalent of HMPA provides a solvent-separated ion pair releasing the steric constraint to ketyl-olefin cyclization. The mechanism derived from rate studies shows that HMPA is important not only in increasing the reduction potential of Sm(II) but also in enhancing the inherent reactivity of the radical anion intermediate formed after electron transfer through conversion of a sterically congested contact ion pair to a solvent-separated ion pair. The mechanistic complexity of the SmI2-HMPA-initiated ketyl-olefin cyclization is driven by the high affinity of HMPA for Sm(III), and these results suggest that simple empirical models describing the role of HMPA in more complex systems are likely to be fraught with a high degree of uncertainty.     

Analysis and evaluation of biobased polyester of PTT/PBAT blend: thermal,dynamic mechanical,interfacial bonding,and morphological properties

Novel blends were prepared from biobased poly(trimethylene terephthalate) (PTT) and poly(butylene adipate‐co‐terephthalate) (PBAT) using a twin screw extrusion process as a function of different weight ratios. Thermal stability, mechanical, and interfacial properties of PTT/PBAT blends were investigated using a thermogravimetric analyzer and mechanical analyzer. Phase behavior and surface morphology of the blends were characterized using scanning electron microscopy. Interfacial bonding value of the PTT/PBAT blend was evaluated from the Pukanszky empirical relationship. Viscoelastic properties of PTT/PBAT blends were investigated using the dynamic mechanical analyzer. PTT/PBAT blend exhibited higher thermal stability than the neat PTT matrix. The entire blend showed better interfacial adhesion between the matrixes. Storage and loss modulus of the PTT/PBAT blend reduces with increasing PBAT content. PTT/PBAT blend exhibited higher impact energy than the neat PTT matrix, because of its flexible and amorphous nature of PBAT polymer and increasing toughness. Copyright © 2016 John Wiley & Sons, Ltd.     

A convenient pathway to Sm(II)-mediated chemistry in acetonitrile

In this communication we show that the instability of samarium diiodide (SmI(2)) in acetonitrile is a consequence of ionization of the reductant in this solvent. Samarium triflate (Sm(OTf)(2)) is exceptionally stable in acetonitrile for periods over six months and can be used with appropriate additives to initiate a ketyl-olefin coupling reaction in high yield.