Synthesis,Characterization and Catalytic Behaviour of Silica Supported Zinc Salicylaldimine Complex

Zinc salicylaldimine complex immobilized on silica gel was used as a promising catalyst for the transesterification reaction of dimethyl terephthalate (DMT) and ethylene glycol (EG).The catalyst was characterized by Fourier transform infra‐red spectroscopy (FT‐IR), thermogravimetric analysis (TGA) and atomic absorption spectroscopy (AAS). The product bis‐(2‐hydroxyethyl)terephthalate (BHET)was confirmed by mass and ¹H‐NMR studies. In comparison to zinc acetate i.e., homogeneous catalyst, a polymer supported catalyst showed better stability, catalytic activity and ease of separation from the reaction product. The catalyst can be reutilized during successive catalytic cycles.     

The standard molar enthalpy of formation of LnPO4(s) (Ln = La, Nd, Sm) by solution calorimetry

The standard molar enthalpy of formation of LaPO₄(s), NdPO₄(s), and SmPO₄(s) has been determined using an isoperibol solution calorimeter. The solution calorimeter vessel was held at 298.15 K. The precipitation reaction between aqueous solution of rare-earth chloride (LnCl₃(aq.)) and ammoniacal solution of ammonium dihydrogen phosphate (NH₄H₂PO₄(aq.)) was studied. The temperature of the calorimeter vessel was measured before, during, and after the reaction. The enthalpy change due to precipitation of LaPO₄(s), NdPO₄(s), or SmPO₄(s) from required solutions was measured at 298.15 K. Using these values and other auxiliary data from the literature, thermochemical reaction scheme were devised to calculate the standard enthalpy of formation of each phosphate compound i.e., LaPO₄(s), NdPO₄(s), and SmPO₄(s). The calculated values for LaPO₄(s), NdPO₄(s), and SmPO₄(s) at 298.15 K were found to be ?1947.5 ± 3.2, ?1938.3 ± 3.6, and ?1942.9 ± 3.4 kJ mol^?1, respectively.     

S‐Alkylation of Soft Scorpionates

The alkylation reactions of soft scorpionates are reported. The hydrotris(S‐alkyl‐methimazolyl)borate dications (alkyl=methyl, allyl, benzyl), which were prepared by the reaction of Tm^Me anion and primary alkyl halides, have been isolated and structurally characterised. The reaction is, however, not universally successful. DFT analysis of these alkylation reactions (C?S versus B? H alkylation) indicates that the observed outcome is driven by kinetic factors. Extending the study to incorporate alternative imine thiones (mercaptobenzothiazole, bz; thiazoline, tz) led to the structural characterisation of di[aquo‐μ‐aquohydrotris(mercaptobenzothiazolyl)boratosodium], which contains sodium atoms in the κ³‐S,S,S coordination mode. Alkylation of Na[Tbz] and Na[tzTtz] leads to decomposition resulting in the formation of the simple S‐alkylated heterocycles. The analysis of the species involved in these reactions shows an inherent weakness in the B? N bond in soft scorpionates, which has implications for their use in more advanced chemistry.     

Direct Evidence of Significantly Different Chemical Behavior and Excited‐State Dynamics of 1,7‐ and 1,6‐Regioisomers of Pyrrolidinyl‐Substituted Perylene Diimide

Novel bay‐functionalized perylene diimides with additional substitution sites close to the perylene core have been prepared by the reaction between 1,7(6)‐dibromoperylene diimide 6 (dibromo‐PDI) and 2‐(benzyloxymethyl)pyrrolidine 5 . Distinct differences in the chemical behaviors of the 1,7‐ and 1,6‐regioisomers have been discerned. While the 1,6‐dibromo‐PDI produced the corresponding 1,6‐bis‐substituted derivative more efficiently, the 1,7‐dibromo‐PDI underwent predominant mono‐debromination, yielding a mono‐substituted PDI along with a small amount of the corresponding 1,7‐bis‐substituted compound. By varying the reaction conditions, a controlled stepwise bis‐substitution of the bromo substituents was also achieved, allowing the direct synthesis of asymmetrical 1,6‐ and 1,7‐PDIs. The compounds were isolated as individual regioisomers. Fullerene (C₆₀) was then covalently linked at the bay region of the newly prepared PDIs. In this way, two separate sets of perylene diimide–fullerene dyads, namely single‐bridged (SB‐1,7‐PDI‐C₆₀ and SB‐1,6‐PDI‐C₆₀) and double‐bridged (DB‐1,7‐PDI‐C₆₀ and DB‐1,6‐PDI‐C₆₀), were synthesized. The fullerene was intentionally attached at the bay region of the PDI to achieve close proximity of the two chromophores and to ensure an efficient photoinduced electron transfer. A detailed study of the photodynamics has revealed that photoinduced electron transfer from the perylene diimide chromophore to the fullerene occurs in all four dyads in polar benzonitrile, and also occurs in the single‐bridged dyads in nonpolar toluene. The process was found to be substantially faster and more efficient in the dyads containing the 1,7‐regioisomer, both for the singly‐ and double‐bridged molecules. In the case of the single‐bridged dyads, SB‐1,7‐PDI‐C₆₀ and SB‐1,6‐PDI‐C₆₀, different relaxation pathways of their charge‐separated states have been discovered. To the best of our knowledge, this is the first observation of photoinduced electron transfer in PDI‐C₆₀ dyads in a nonpolar medium.     

Stereoselective tandem synthesis of oxazolo-fused pyrroloquinolines from o-alkynylaldehydes via Ag(I)-catalyzed regioselective 5-exo-dig ring closure

A tandem approach for the regio- and stereoselective synthesis of oxazolo-fused pyrroloquinolines 3a–l via the reaction of o-alkynylaldehydes 1a–i with chiral amino alcohols 2a–c under mild reaction conditions is described. The possible participation of the pyridine ring in the regioselective formation of 5-exo-dig cyclized products was supported by the controlled experiments. The structures and stereochemistry of the products were confirmed by NOESY and X-ray crystallographic studies.     

Levels and effects of natural radionuclides in soil samples of Garhwal Himalaya

Distribution of natural radionuclide gives significant parameter to assess the presence of gamma radioactivity and its radiological effect in our environment. Natural radionuclides are present in the form of ²²⁶Ra, ²³²Th and ⁴⁰K in soil, rocks, water, air, and building materials. Distribution of natural radionuclides depends on the type of minerals present in the soil and rocks. For this purpose gamma spectrometer is used as tool for finding the concentration of these radionuclides. The activity concentration of naturally occurring radionuclides ²²⁶Ra, ²³²Th and ⁴⁰K in these soil samples were found to vary from of 8 ± 1 Bq/kg to 50 ± 10 Bq/kg with an average 20 Bq/kg, 7 ± 1–88 ± 16 Bq/kg with an Average 26 Bq/kg and 115 ± 18–885 ± 132 Bq/kg with an average 329 Bq/kg, respectively. In this paper, we are presenting the radiological effect due to distribution of natural radionuclide present in soil of Garhwal Himalaya.     

Redox-Switchable Complexes Based on Nanographene-NHCs

A series of rhodium and iridium complexes with a N-heterocyclic carbene (NHC) ligand decorated with a perylene-diimide-pyrene moiety are described. Electrochemical studies reveal that the complexes can undergo two successive one-electron reduction events, associated to the reduction of the PDI moiety attached to the NHC ligand. The reduction of the ligand produces a significant increase on its electron-donating character, as observed from the infrared spectroelectrochemical studies. The rhodium complex was tested in the [3+2] cycloaddition of diphenylcyclopropenone and methylphenylacetylene, where it displayed a redox-switchable behavior. The neutral complex showed moderate activity, which was suppressed when the catalyst was reduced.     

Cerium oxide-catalyzed multicomponent condensation approach to spirooxindoles in water

An efficient and facile green synthesis of spirooxindole derivatives bearing pyrano[2,3-c]pyrazole moiety has been achieved via a \(\mathrm{CeO}_{2}\)-NPs catalyzed four-component reaction in water. The protocol offers an environmentally benign and effective approach to highly functionalized and biologically interesting spiro[indoline-3,4\(^\prime \)-pyrano[2,3-c]pyrazole] derivatives. The synthesized compounds exhibit potent antioxidant and antibacterial activities.     

Structural phase transition of vanadium at 69 GPa

A phase transition was observed at 63-69 GPa and room temperature in vanadium with synchrotron x-ray diffraction. The transition is characterized as a rhombohedral lattice distortion of the body-centered-cubic vanadium without a discontinuity in the pressure-volume data, thus representing a novel type of transition that has never been observed in elements. Instead of driven by the conventional s-d electronic transition mechanism, the phase transition could be associated with the softening of C44 trigonal elasticity tensor that originates from the combination of Fermi surface nesting, band Jahn-Teller distortion, and electronic topological transition.     

Femtosecond laser erasing and rewriting of self-organized planar nanocracks in fused silica glass

Tightly focused, linearly polarized, femtosecond laser radiation can produce highly birefringent nanograting structures inside fused silica glass. Here we report that when the polarization direction of the femtosecond light is changed, old nanogratings are erased and simultaneously replaced with new ones whose orientation is solely determined by the polarization of the rewrite beam. We also show that these volume nanogratings can be rewritten 1000 times with little degradation in their quality.