Spectroscopic Study of Azo- and Azoxycrowns Binding with Cations of Similar Ionic Radius

The complexation of 13- and 16-memberedazo- and azoxycrowns with metal cations of similarionic diameter (Na⁺ and Ca²⁺; and K⁺,Ba²⁺, Ag⁺ and Pb²⁺) was studied byuv/visible spectroscopic titration in acetonitrile andMeOH. In MeOH the 13-membered azo- and azoxycrowns 1 and 2 are weakly and non-selectively bound tohard cations of similar ionic diameter, but differentcharge (Na⁺ and Ca²⁺). At the same time thebinding to the soft cation Ag⁺ of larger sizethan the macrocycle cavity is considerably stronger.In contrast to solutions in acetonitrile no bindingwith the small Li⁺ cation was found.The 16-membered azocrowns 3 and 4 alsodiscriminate silver cation in MeOH withlog K = 3.65 ± 0.1 for both compounds.Unexpectedly low bindingwith the hard barium divalent cation of similar size(log K = 1.55 ± 0.4 and 1.95 ± 0.2, respectively)was found for these compounds. Similarly to13-membered compounds no binding with the smallLi⁺ cation was detected. A reverse order ofselectivity was observed for these crowns inacetonitrile with binding constant for association of3 with Ba²⁺ (log K 5.3) considerablyhigher than for other cations. The previously observedstrong binding with the smaller Li⁺ and Na⁺cations is confirmed.     

Geometries and NMR properties of cisplatin and transplatin revisited at the four-component relativistic level

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Theory of the transition from conductive to convective burning

The experimentally known phenomenon of an abrupt transition from slow conductive to fast convective (penetrative) burning in a confined gas-permeable explosive is discussed. A simple model, involving only the most essential physical ingredients, is formulated and analyzed. A good qualitative agreement between theoretical and experimental dependencies is obtained. The transition is triggered by a localized autoignition in the extended resistance-induced preheat zone formed ahead of the advancing deflagration, provided the pressure difference between hot gas products and gases deep inside the pores of the unburned solid exceeds a certain critical level. In line with observations the critical overpressure increases with diminishing permeability.     

A comparison of numerical and analytical radiative-transfer solutions for plane albedo of natural waters

Several numerical and analytical solutions of the radiative transfer equation (RTE) were compared for plane albedo in a problem of solar light reflection by sea water. The study incorporated the simplest case—a semi-infinite one-dimensional plane—parallel absorbing and scattering homogeneous layer illuminated by a monodirectional light beam. Inelastic processes (such as Raman scattering and fluorescence), polarization and air-water surface refraction-reflection effects, were not considered. Algorithms were based on the invariant imbedding method and two different variants of the discrete ordinate method (DOM). Calculations were performed using parameters across all possible ranges (single-scattering albedo ω₀ and refracted solar zenith angle θ₁), but with a special emphasis on natural waters. All computations were made for two scattering phase functions, which included an almost isotropic Rayleigh phase function and strongly anisotropic double-peaked Fournier-Forand-Mobley phase function. Models were validated using quasi-single-scattering (QSSA) and exponential approximations, which represent the extreme cases of ω₀→0 and ω₀→1, respectively. All methods yielded relative differences within 1.8% for modeled natural waters. An analysis of plane albedo behavior resulted in the development of a new extended QSSA approximation, which when applied in conjunction with the extended Hapke approximation developed earlier, resulted in a maximum relative error of 2.7%. The study results demonstrated that for practical applications, the estimation of inherent optical properties from observed reflectance can best be achieved using an extended Hapke approximation.     

The Use of tert-Butyl Vinyl Ether in Stepwise Electrophilic Addition Reactions

tert-Butyl vinyl ether (1) reacts with p-TolSCl to give 2-tert-butoxy-2-chloroethyl p-tolyl sulfide (2). In the presence of SnCl₄, 2 reacts with silyl enol ethers, allyltrimethylsilane, and vinyl ethers to form a C-C bond. In the case of vinyl ethers, the reaction proceeds through the formation of the 5-membered sulfonium salt intermediate which in turn can react with H₂O, TMSCN, allyltrimethylsilane, and Grignard reagents.     

Synthesis and Crystal Structure of LiY(CN2)2, Having a Structure Related to That of NiAs

The new ternary carbodiimide LiY(CN₂)₂ was synthesized by solid state metathesis reaction between YF₃ and Li₂(CN₂) in a silica tube at 550 °C. The X‐ray single‐crystal structure determination yielded an orthorhombic crystal system (Pbcn, Z = 4, a = 982.0(3), b = 698.5(2), c = 613.4(2) pm). The crystal structure can be considered related to the NiAs structure. The carbodiimide ions are arranged in layers following the motif of a hexagonal closest packing of sticks. Lithium and yttrium cations occupy all octahedral voids in an ordered fashion, alternating on top of each other along the hcp stacking direction.     

Atom-economic Approach to the Synthesis of α-(Hetero)aryl-substituted Furan Derivatives from Biomass

An atom-economic ring construction approach to the synthesis of α-(hetero)arylfurans based on renewable furanic platform chemicals has been developed. Corresponding compounds have been prepared in good to excellent yields via [2+2+2] and [4+2] cycloaddition reactions using metal-catalyzed or photoredox protocols. Easily available HMF-based 2-hydroxymethyl-5-ethynylfuran and 2-hydroxymethyl-5-cyanofuran were used as starting materials. A synthetic route with an improved carbon economy factor has been implemented to achieve sustainability aim. The possible application of arylfurans as molecular conductors has been investigated by DFT calculations, which revealed excellent charge transfer properties. As a future perspective, integration of biomass processing strategy into manufacturing of molecular electronics was pointed out to achieve the aim of sustainability.