Design of crystal packings of styrylheterocycles and [2+2] photocycloaddition reactions in their single crystals 7. Crystal structures of 4-styrylpyridine hydroperchlorates and solid-state [2+2] autophotocycloaddition reactions of these compounds

A series of 4-styrylpyridine hydroperchlorates were synthesized, and the [2+2] autophotocycloaddition (PCA) reaction in their polycrystalline films and single crystals resulting in the centrosymmetric rctt isomers of 1,2,3,4-tetrasubstituted cyclobutanes was investigated. Unlike neutral styrylpyridines, their protonated forms are better preorganized for the solid-state PCA reaction. According to the X-ray diffraction data, the cations of these compounds, like related styryl dyes, are mainly stacked in crystals in a head-to-head or head-to-tail fashion with equal probability. Only in the latter type of stacks, the PCA reaction is feasible as a single-crystal-to-single-crystal transformation. The crystal packing is stabilized by hydrogen bonds between organic cations and perchlorate anions, as well as by other weak directional interactions, for example, by S??S interactions, thus preventing the atomic displacements in the course of PCA. The completion of the PCA reaction in single crystals without their degradation was observed only for 15-crown-5-containing 4-styrylpyridine hydroperchlorate. The crystals of the latter compound are stabilized not by hydrogen bonds between the cations and anions but by N⁺-H??O(macrocycle) hydrogen bonds resulting in the formation of head-to-tail stacked dimers. In the crystals, these dimers are surrounded by a soft shell formed by rotationally and translationally mobile anions and benzene solvent molecules, as well as by conformationally flexible crown-ether moieties of adjacent dimer pairs. This leads to a decrease in the steric strain that occurs in the crystals in the course of PCA and prevents the degradation of single crystals. The PCA reaction is accompanied by the reduction in the crystal symmetry due to the doubling of the unit cell.     

Cu(II)-alkyl chlorocomplexes: stable compounds or transients? DFT prediction of their structure and EPR parameters

DFT calculations were used for studying the structure and reactivity of organocuprates(II) usually considered as intermediates with very weak Cu-C bond. It was found that calculated principal g-tensor values of model compounds RCu(II)Cl(2(-)) are similar to the experimentally found values for organocopper product of photolysis of quaternary ammonium tetrachlorocuprates. The calculations confirm that the most of organocuprates(II) could be stable at ambient conditions, and short lifetimes of organocuprates(II) in solutions or soft matrices are caused by their high reactivity in various bimolecular processes; the rate of those may be close to the rate of diffusion controlled reactions. The charges, spin densities, and d-orbital populations of the Cu atom in them are typical for bivalent copper complexes. Natural bond orbital analysis of organochlorocuprates(II) confirms the formation of polar σ-bond between copper and carbon atoms.     

Mechanism of the conductivity and sensor response of nanostructured In2O3+ZnO films

The conductivity and sensor properties of mixed nanostructured In₂O₃+ZnO metal oxide systems with different component ratios are investigated. It is found that maximum sensor sensitivity in detecting hydrogen and CO in composite films containing 15 and 80 wt % In₂O₃ considerably exceeds the sensitivity of individual oxides. A mechanism of the sensor action, which is largely determined by the dependency of the paths of conductivity in a composite metal-oxide film on its composition, is proposed. It is established that the main factors determining the conductivity and sensor sensitivity of In₂O₃ + ZnO composite are modifications in the electron structure of crystals (mainly by In₂O₃) during the formation of composites, electron transfer from In₂O₃ to ZnO, and the catalytic activity of ZnO. It is shown in particular that ZnO effectively catalyzes the reaction of hydrogen dissociation and, in contact with In₂O₃, favors the chemical sensibilization of the sensor response of such mixed metal oxide systems in detecting H₂ and CO.     

Sensors based on SnO<Subscript>2</Subscript> + In<Subscript>2</Subscript>O<Subscript>3</Subscript> composite films for detecting CO in air

The sensor properties of nanostructured films of SnO₂, In₂O₃, and their combinations for detecting CO in air in the temperature range of 330–520°C were investigated. It was found that SnO₂ films show the least sensitivity to CO. Sensitivity grows as the concentration of In₂O₃ in SnO₂ increases, and it reaches its maximum value in pure In₂O₃. At the same time, the maximum of sensitivity to CO in air shifts towards low temperatures. Sensor response time was found to be about 1 s for the studied SnO₂ and In₂O₃ films, and about 0.5 s for the composite film. The mechanism of sensor sensitivity for the studied metal oxide films in detecting CO in air is discussed.     

Synthesis, structure, and properties of supramolecular charge-transfer complexes between bis(18-crown-6)stilbene and ammonioalkyl derivatives of 4,4'-bipyridine and 2,7-diazapyrene

4,4'-Bipyridine and 2,7-diazapyrene derivatives (A) having two ammonioalkyl N-substituents were synthesized. The complex formation of these compounds with bis(18-crown-6)stilbene (D) was studied by spectrophotometry, cyclic voltammetry, (1)H NMR spectroscopy, and X-ray diffraction analysis. In MeCN, π-donor D and π-acceptors A form supramolecular 1:1 (D·A) and 2:1 (D·A·D) charge-transfer complexes. The D·A complexes have a pseudocyclic structure as a result of ditopic binding of the ammonium groups to the crown-ether fragments. The better the geometric matching between the components, the higher the stability of the D·A complexes (log K up to 9.39). A key driving force of the D·A·D complex formation is the excessive steric strain in the precursor D·A complexes. The pseudocyclic D·A complexes involving the ammoniopropyl derivative of 4,4'-bipyridine were obtained as single crystals. Crystallization of the related ammonioethyl derivative was accompanied by transition of the D·A complexes to a structure of the (D·A)(m) coordination polymer type.     

Generation of MeV photons and protons in laser picosecond plasmas

The results of experiments devoted to studying the generation of MeV photons and protons in picosecond laser plasmas at a laser beam intensity of 10¹⁸ W/cm² on Be, Ta, LiF and H⁷Li targets are presented. Nuclear reactions (γ, n) and (p, n) were used to detect MeV photons and protons. The number of MeV photons and protons generated in laser plasmas was found from the measured neutron yield. Possibilities of particle acceleration due to the formation of pinch structures in laser plasmas are discussed. Calculated and experimental results are compared.     

Analog of Electroweak model for contracted gauge group

The limiting case of the bosonic part of the standard Electroweak Model, which corresponds to the contracted gauge group SU(@#@ 2; j) × U(1) is discussed. The Higgs-boson, Z-boson, and electromagnetic fields become external ones with respect to the W-boson fields. The W-boson fields do not affect these external fields. The masses of all particles of the Electroweak Model remain the same under contraction.     

Electron Diffraction Analysis of the Structure of Carbon Nanopillars along the Growth Direction

The structure of carbon nanopillars grown without catalysis by low-temperature plasmaenhanced-chemical-vapor deposition on a silicon substrate is investigated using the suggested focused ion beam technique for preparing a sample composed of several thin plan-view foils. Studying the prepared sample by electron diffraction and bright-field transmission electron microscopy allows determination of the variation of the two-dimensionally ordered crystallite fraction along the growth direction. It us established that the crystalline phase fraction inside the nanopillars gradually decreases during the growth process. Nearly 90% of the crystalline material is located between the base and the middle of the nanopillars while their upper parts almost entirely consist of amorphous carbon.     

The structure of optimal solutions for harvesting a renewable resource

We consider the problem of optimal harvesting of a renewable resource whose dynamics are governed by logistic growth and whose payoff is proportional to the harvest. We consider both the case of a finite and an infinite time horizon and analyse the structure of the optimal solutions and their dependence on the parameters of the model. We show that the optimal policy can only have one of three structures: (1) maximal harvesting effort until the resource is depleted, (2) zero harvesting during an initial time interval followed by a subsequent switch to maximal harvesting effort, or (3) a singular solution, which corresponds to an intermediate level of harvesting, accompanied by the most rapid approach path. All three scenarios emerge, with minor variations, with finite and infinite time horizons, depending on the particular combination of parameters of the system. We characterize the conditions under which the singular solution is optimal and present suggestions for designing an optimal and sustainable harvesting strategy. Recommendations for Resource Managers :

• We have rigorously explored a standard optimal harvesting model and its steady states.
• We show that three different types of solutions may emerge: (i) maximal harvesting eventually leading to a complete depletion of the stock; (ii) maximal harvesting with a potential period of idleness leading to a positive stock; (iii) an initial phase of either no or full harvesting followed by a period of intermediate harvesting intensity leading to a positive stock (singular solution).
• With some modifications, similar results hold for a finite planning horizon.
• Which of these three scenarios emerges in the finite horizon case depends not only on the parameter values but also on the length of the planning horizon.