Cationic Organophosphorus Chromophores: A Diamond in the Rough among Ionic Dyes

Tunable electron-accepting properties of the cationic phosphorus center, its geometry and unique preparative chemistry that allows combining this unit with diversity of π-conjugated motifs, define the appealing photophysical and electrochemical characteristics of organophosphorus ionic chromophores. This Minireview summarizes the achievements in the synthesis of the π-extended molecules functionalized with P-cationic fragments, modulation of their properties by means of structural modification, and emphasizes the important effect of cation-anion interactions, which can drastically change physical behavior of these two-component systems.     

Interface Amorphization of Two-Dimensional Black Phosphorus upon Treatment with Diazonium Salts

Two-dimensional (2D) black phosphorus (BP) represents one of the most appealing 2D materials due to its electronic, optical, and chemical properties. Many strategies have been pursued to face its environmental instability, covalent functionalization being one of the most promising. However, the extremely low functionalization degrees and the limitations in proving the nature of the covalent functionalization still represent challenges in many of these sheet architectures reported to date. Here we shine light on the structural evolution of 2D-BP upon the addition of electrophilic diazonium salts. We demonstrated the absence of covalent functionalization in both the neutral and the reductive routes, observing in the latter case an unexpected interface conversion of BP to red phosphorus (RP), as characterized by Raman, ³¹P-MAS NMR, and X-ray photoelectron spectroscopies (XPS). Furthermore, thermogravimetric analysis coupled to gas chromatography and mass spectrometry (TG-GC-MS), as well as electron paramagnetic resonance (EPR) gave insights into the potential underlying radical mechanism, suggesting a Sandmeyer-like reaction.     

Photophysics of Azobenzene Constrained in a UiO Metal–Organic Framework: Effects of Pressure,Solvation and Dynamic Disorder

Photophysical studies of chromophoric linkers in metal–organic frameworks (MOFs) are undertaken commonly in the context of sensing applications, in search of readily observable changes of optical properties in response to external stimuli. The advantages of the MOF construct as a platform for investigating fundamental photophysical behaviour have been somewhat overlooked. The linker framework offers a unique environment in which the chromophore is geometrically constrained and its structure can be determined crystallographically, but it exists in spatial isolation, unperturbed by inter-chromophore interactions. Furthermore, high-pressure studies enable the photophysical consequences of controlled, incremental changes in local environment or conformation to be observed and correlated with structural data. This approach is demonstrated in the present study of the trans-azobenzene chromophore, constrained in the form of the 4,4’-azobenzenedicarboxylate (abdc) linker, in a UiO topology framework. Previously unobserved effects of pressure-induced solvation and conformational distortion on the lowest energy, nπ* transition are reported, and interpreted the light of crystallographic data. It was found that trans-azobenzene remains non-fluorescent (with a quantum yield less than 10⁻⁴) despite the prevention of trans-cis isomerization by the constraining MOF structure. We propose that efficient non-radiative decay is mediated by the local, pedal-like twisting of the azo group that is evident as dynamic disorder in the crystal structure.     

Non-integrability vs. integrability in pentagram maps

We revisit recent results on integrable cases for higher-dimensional generalizations of the 2D pentagram map: short-diagonal, dented, deep-dented, and corrugated versions, and define a universal class of pentagram maps, which are proved to possess projective duality. We show that in many cases the pentagram map cannot be included into integrable flows as a time-one map, and discuss how the corresponding notion of discrete integrability can be extended to include jumps between invariant tori. We also present a numerical evidence that certain generalizations of the integrable 2D pentagram map are non-integrable and present a conjecture for a necessary condition of their discrete integrability.     

Topological monodromy as an obstruction to Hamiltonization of nonholonomic systems: Pro or contra?

The phenomenon of a topological monodromy in integrable Hamiltonian and nonholonomic systems is discussed. An efficient method for computing and visualizing the monodromy is developed. The comparative analysis of the topological monodromy is given for the rolling ellipsoid of revolution problem in two cases, namely, on a smooth and on a rough plane. The first of these systems is Hamiltonian, the second is nonholonomic. We show that, from the viewpoint of monodromy, there is no difference between the two systems, and thus disprove the conjecture by Cushman and Duistermaat stating that the topological monodromy gives a topological obstruction for Hamiltonization of the rolling ellipsoid of revolution on a rough plane.     

The investigation of neutralization process of gas-phase sewage sludge using thermal plasma method

The purpose of this research is to investigate the influence of plasma flow on the composition of gaseous phase organic waste. The experimental method and simulation program “Chemical Workbench” were used for this research. The gas phase waste was neutralized using air plasma in the temperature range of 1200–1700 K. The reactor simulation results showed that the amount of atomic oxygen and nitrogen decreases by 0.5%, meanwhile the amount of carbon monoxide increases by 0.5 percent, as the plasma forming gas is air. The investigation of percentage concentration results showed that as the temperature reaches 1700 K, the H₂ decreases by 4%, CO increases by 7%, CH₄ decreases by 0.4%, CO increases by 0.5%, N₂ decreases by 5%. The experimental measurement results of percentage concentration correlates sufficiently with simulation results for listed gas.