Crystal Multi‐Conformational Control Through Deformable Carbon‐Sulfur Bond for Singlet‐Triplet Emissive Tuning

Crystal‐state luminophores have been of great interest in optoelectronics for years, whereas the excited state regulation at the crystal level is still restricted by the lack of control ways. We report that the singlet‐triplet emissive property can be profoundly regulated by crystal conformational distortions. Employing fluoro‐substituted tetrakis(arylthio)benzene luminophores as prototype, we found that couples of molecular conformations formed during different crystallizations. The deformable carbon‐sulphur bond essentially drove the distortion of the molecular conformation and varied the stacking mode, together with diverse non‐covalent interactions, leading to the proportional adjustment of the fluorescence and phosphorescence bands. This intrinsic strategy was further applied for solid‐state multicolor emissive conversion and mechanoluminescence, probably offering new insights for design of smart crystal luminescent materials.     

Structural Evolution of Diisopropylammonium Chloride (DIPAC) Molecular Ferroelectric

Physics of the Solid State - Room-temperature changes in the structure of a new diisopropylammonium chloride (C6H16ClN, DIPAC) molecular ferroelectric have been investigated by high-resolution...     

About using the approximate fields to calculate the electrostatic potential distribution of membrane channels

By the example of gramicidine channel, a comparative analysis of different approximate representations (heavy atoms, polar protons, near-by atoms) of AMBER force field has been carried out to calculate the electrostatic potential distribution of ionic channels in biological membranes. The results obtained are compared with the potential computed in a full-atom representation. The use of approximate representations is shown to lead to estimated errors of the potential.     

Theoretical study of the models of Ca2+ and Mg2+ ions binding by the methylidene rhodanine neutral and anionic forms

The equilibrium geometry and energy parameters of the complexes of Ca²⁺ and Mg²⁺ with 5-methyl-2-thioxotiazolidin-4-one (methylidene rhodanine) and its anion in a 1:1 ratio in different conformations were calculated by the quantum-chemical method with the density functional theory on the level of hybrid functional B3LYP in the basis of atomic orbitals 6–31+G(d). The influence of metal ion size on the number of possible isomeric coordinations was indicated. The principles of stabilization and destabilization of the structures depending on their conformations al structure were described. Based on the calculated equilibrium geometry parameters of the complexes conformations the effect of complexation on the structure of rhodanine ligand was elucidated. In the framework of a polarizable continuum the relative stability of the possible tautomeric forms of methylidene rhodanine in water was investigated. A new structure of the methylidene rhodanine anion distinquished by a specific distribution of negative charge is suggested.     

Studies of nanoporous matrices filled with sodium nitrite by nonlinear dielectric spectroscopy

Variation of nanocrystalline NaNO₂ properties was studied under the conditions of confined geometry by nonlinear dielectric spectroscopy. It was shown that a decrease in the pore size of silicate matrices MCM-41 filled with NaNO₂ leads to an increase of nonlinearity and a change in the shape of the curves of the third harmonic amplitude as a function of temperature.     

Terahertz and infrared photodetectors based on multiple graphene layer and nanoribbon structures

We consider new concepts of terahertz and infrared photodetectors based on multiple graphene layer and multiple graphene nanoribbon structures and we evaluate their responsivity and detectivity. The performance of the detectors under consideration is compared with that of photodetectors made of the traditional structures. We show that due to high values of the quantum efficiency and relatively low rates of thermogeneration, the graphene-based detectors can exhibit high responsivity and detectivity at elevated temperatures in a wide radiation spectrum and can substantially surpass other detectors. The detector being discussed can be used in different wide-band and multi-colour terahertz and infrared systems.     

Specific features of the dielectric response of heterogeneous systems with a polar matrix containing electrically active inclusions

A theoretical model has been proposed which makes it possible to introduce the correction into the complex permittivity of electrically active condensed systems that contain a polar liquid matrix and low-dimensional solid particles with a developed electrically active surface. It has been established that there is an interfacial electrical interaction between surface charges of the solid component and polar molecules of the liquid matrix. The processes occurring during this interaction lead to the appearance of an intrinsic internal electric field in the system under investigation. The contribution from surface effects to the formation of the polarized state of the polar liquid medium has been investigated in terms of the proposed model. The possibility of controlling the processes of local change in the structure of the polar liquid component under the effect of the internal electric field by varying the electrically active specific surface area of the solid phase and the intrinsic dipole moment of molecules of the liquid matrix has been analyzed in the studied systems. The conditions providing for the appearance of a controlled potential gradient of the internal electric field have been determined for the dispersed systems under consideration. The parameter that makes it possible to evaluate the contribution from the interfacial electrical contact interaction to the dielectric response of the liquid component and the entire system has been introduced for the first time.     

Analysis of the structural interaction of electrically active heterogeneous finely dispersed systems at the interfaces between the solid and liquid phases

Strong electrical forces have been revealed in electrically active heterogeneous finely dispersed systems at the interfaces between the solid and liquid phases. It has been established that these forces give rise to gradients of the potential of an internal self-electric field that can provide circulation of electric currents in the systems under investigation. It has been found that, in these systems, there arises a double electric layer that represents a new structuring phase, which is characteristic of electrically active systems only. The mechanism of formation of a double electric layer includes electrocontact interaction between the surfaces of two heterogeneous liquid and solid polar dielectrics.     

Anti‐Aromatic versus Induced Paratropicity: Synthesis and Interrogation of a Dihydro‐diazatrioxa[9]circulene with a Proton Placed Directly above the Central Ring

We present a high‐yielding intramolecular oxidative coupling within a diazadioxa[10]helicene to give a dihydro‐diazatrioxa[9]circulene. This is the first [n]circulene containing more than eight ortho‐annulated rings (n>8). The single‐crystal X‐ray structure reveals a tight columnar packing, with a proton from a pendant naphthalene moiety centred directly above the central nine‐membered ring. This distinct environment induces a significant magnetic deshielding effect on that particular proton as determined by ¹H NMR spectroscopy. The origin of the deshielding effect was investigated computationally in terms of the NICS values. It is established that the deshielding effect originates from an induced paratropic ring current from the seven aromatic rings of the [9]circulene structure, and is not due to the nine‐membered ring being antiaromatic. UV/Vis spectroscopy reveals more efficient conjugation in the prepared diazatrioxa[9]circulene compared to the parent helical azaoxa[10]helicenes, and DFT calculations, including energy levels, confirm the experimental observations.     

Phase transitions in KNO3 embedded in MCM-41 films with regular nanopores

This paper reports on a comparative study of phase transitions in nanocomposites made up of KNO₃ embedded in 10-μm-thick MCM-41 films with unidirectional pores 4.0 nm in size on an aluminum substrate and of nanocomposites prepared in the form of potassium-nitrate-filled pressed MCM-41 powders with 3.7-nm pores. The temperature dependences of linear permittivity and the amplitude of third harmonic generation have been measured under heating and cooling. The structural transition from phase II to phase I shifts under heating relative to that occurring in bulk KNO₃ toward lower temperatures for potassium nitrate in the film and toward higher temperatures for the pressed MCM-41-based nanocomposite. A significant difference has been observed also within the region of existence of ferroelectric phase III. The data obtained suggest that the shifts of phase transition temperatures observed in the conditions of nanoconfinement are influenced markedly not only by pore size and geometry but also by other factors.