Photochemical generation of nitrenium ions from protonated 1,1-diarylhydrazines

[reaction: see text] Laser flash photolysis experiments, chemical trapping studies, and time-dependent density functional theory calculations demonstrate that photolysis of protonated 1,1-diarylhydrazines generates N,N-diarylnitrenium ions.     

Metallocanes of group 14 elements. 1. Derivatives of silicon and germanium. (Review)

Results on the synthesis of silocanes and germocanes, eight-membered heterocycles with the general formula D(CH₂CH₂Z)₂MXY are analyzed and classified. The chemical behavior of these compounds and the characteristics of the element-nitrogen transannular bond are studied. Dedicated to Prof. E. Lukevics on his 70th birthday. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1777–1825, December, 2006.     

Metallocanes of group 14 elements 2. Derivatives of tin (Review)

Results on the synthesis of stannocanes-eight-membered heterocycles with the general formula D(CH₂CH₂Z)₂SnXY-are reviewed and analyzed. The chemical behavior of the compounds is examined, and the nature of the transannular bond is studied. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 963–991, July, 2007.     

Highly Crystalline and Semiconducting Imine‐Based Two‐Dimensional Polymers Enabled by Interfacial Synthesis

Single‐layer and multi‐layer 2D polyimine films have been achieved through interfacial synthesis methods. However, it remains a great challenge to achieve the maximum degree of crystallinity in the 2D polyimines, which largely limits the long‐range transport properties. Here we employ a surfactant‐monolayer‐assisted interfacial synthesis (SMAIS) method for the successful preparation of porphyrin and triazine containing polyimine‐based 2D polymer (PI‐2DP) films with square and hexagonal lattices, respectively. The synthetic PI‐2DP films are featured with polycrystalline multilayers with tunable thickness from 6 to 200 nm and large crystalline domains (100–150 nm in size). Intrigued by high crystallinity and the presence of electroactive porphyrin moieties, the optoelectronic properties of PI‐2DP are investigated by time‐resolved terahertz spectroscopy. Typically, the porphyrin‐based PI‐2DP 1 film exhibits a p‐type semiconductor behavior with a band gap of 1.38 eV and hole mobility as high as 0.01 cm² V^?1 s^?1, superior to the previously reported polyimine based materials.     

Theoretical and Experimental Analysis of the Reaction Mechanism of MrTPS2, a Triquinane‐Forming Sesquiterpene Synthase from Chamomile

Terpene synthases, as key enzymes of terpene biosynthesis, have garnered the attention of chemists and biologists for many years. Their carbocationic reaction mechanisms are responsible for the huge variety of terpene structures in nature. These mechanisms are amenable to study by using classical biochemical approaches as well as computational analysis, and in this study we combine quantum‐chemical calculations and deuterium‐labeling experiments to elucidate the reaction mechanism of a triquinane forming sesquiterpene synthase from chamomile. Our results suggest that the reaction from farnesyl diphosphate to triquinanes proceeds through caryophyllyl and presilphiperfolanyl cations and involves the protonation of a stable (?)‐(E)‐β‐caryophyllene intermediate. A tyrosine residue was identified that appears to be involved in the proton‐transfer process.     

X-ray,optical and electrical study of melt-grown CdI2 single crystals

CdI₂ has been purified using the zone-refining technique by giving 20 passes. Single crystals grown from the starting material showed arcing in the X-ray oscillation photographs whereas it is absent in the crystals grown from the zone refined material. These crystals are found to be of the 4 H type. DC conductivity studies were made on these crystals at various stages of purification. The surface morphology of these crystals have been studied using an optical microscope.     

Trialkoxysilane Exchange: Scope,Mechanism, Cryptates and pH-Response

The dynamic covalent chemistry (DCvC) of the Si−O bond holds unique opportunities, but has rarely been employed to assemble discrete molecular architectures. This may be due to the harsh conditions required to initiate exchange reactions at silicon in aprotic solvents. Herein, we provide a comprehensive experimental and computational account on the reaction of trialkoxysilanes with alcohols and identify mild conditions for rapid exchange in aprotic solvents. Substituent, solvent and salt effects are uncovered, understood and exploited for the construction of sila-orthoester cryptates. A sharp, divergent pH-response of the obtained cages renders this substance class attractive for future applications well beyond host-guest chemistry, for instance, in drug delivery.