Maxim A. Shcherbina

Thermotropic columnar mesophases of wedge‐shaped benzenesulfonic acid mesogens

The synthesis and characterisation are reported of two groups of new amphiphilic sulfonate compounds, 2,3,4‐tris(dodecyloxy)benzenesulfonates, 2,3,4‐tris(dodecyloxy)benzenesulfonamide and the isomeric 3,4,5‐tris(dodecyloxy)benzenesulfonates. As revealed by a combination of thermo‐optical microscopy, differential scanning calorimetry and X‐ray scattering techniques, the occurrence of mesophases is controlled by the radius of the cation and the symmetry of the molecule. The sulfonates exhibited a rich phase behaviour involving cubic, ordered and disordered columnar mesophases, depending on the counter ion and the type of substitution. It is proposed that the term ‘cunitic’ molecules should be introduced as a class descriptor for wedge‐shaped molecules and their columnar phases.

Structure of gyroid mesophase formed by monodendrons with fluorinated alkyl tails

The structure of a three-dimensional mesophase has been studied by the methods of small-angle X-ray diffraction and reconstruction of electron-density maps of the cubic lattice. In the oriented samples based on monodendrons with partially fluorinated alkyl tails, this mesophase has been shown to coexist with a two-dimensional columnar phase through a wide temperature interval. Epitaxial relationships between (10) planes of the hexagonal lattice and (211) planes of the cubic lattices lead to the ten-point pattern of azimuthal intensity distribution for the first X-ray 211 reflection and to the six-point intensity distribution for the second 220 reflection. The observed 12-point pattern of the 220 reflection is due to the presence of twin “crystallites” of the three-dimensional phase, and their [110] axis is parallel to the axis of cylinders in the columnar phase. The reconstructed electron-density maps show that the regions with increased electron density, which are composed of fluorinated aliphatic tails, form a bicontinuous gyroid structure.

Effects of oligothiophene π-bridge length on physical and photovoltaic properties of star-shaped molecules for bulk heterojunction solar cells

The preparation of four different star-shaped donor (D)–π–acceptor (A) small molecules (N(Ph-1T-DCN-Me)3, N(Ph-2T-DCN-Me)3, N(Ph-2T-DCN-Hex)3 and N(Ph-3T-DCN-Hex)3) possessing various oligothiophene π-bridge lengths and their use in solution-processed bulk heterojunction small molecule solar cells is reported. Optical and electrochemical data show that increasing oligothiophene π-bridge length leads to a decrease of the optical band gap due to a parallel increase of the highest occupied molecular orbital (HOMO) level. Furthermore, subtle modifications of a molecular π-bridge length strongly affect the thermal behavior, solubility, crystallization, film morphology and charge carrier mobility, which in turn significantly change the device performance. Although the moderately increasing oligothiophene π-bridge length uplifts the HOMO level, it nevertheless induces an increase of the efficiency of the resulting solar cells due to a simultaneous improvement of the short circuit current (Jsc) and fill factor (FF). The study demonstrates that such an approach can represent an interesting tool for the effective modulation of the photovoltaic properties of the organic solar cells (OSCs) at a moderate cost.

Star-shaped D–π–A oligothiophenes with a tris(2-methoxyphenyl)amine core and alkyldicyanovinyl groups: synthesis and physical and photovoltaic properties

Synthesis of a series of star-shaped oligomers having a novel electron donating tris(2-methoxyphenyl)amine (m-TPA) core, which is linked through a bithiophene or terthiophene π-bridge with electron-deficient alkyldicyanovinyl (alkyl-DCV) groups, is described. A comprehensive study of the oligomers revealed significant dependence of their physical properties, including absorption, molecular frontier energy levels, crystal packing, and melting and glass transition temperatures, upon the chemical structure. A comparison of their photophysical properties to the nearest analog having the common dicyanovinyl (DCV) groups demonstrated a number of benefits to use alkyl-DCV units for the design of donor–acceptor small molecules: higher solubility, increased electrochemical stability, better photovoltaic performance, and possibility to control the relative physical and photovoltaic properties by a simple adjustment of alkyl and π-bridge lengths. Modification of the well-known triphenylamine (TPA) core in the star-shaped oligomers by methoxy groups increases not only solubility, but also crystallinity of the oligomers, whereas their photovoltaic performance stays on a similar level as their analogs with a TPA core. The study demonstrates that these design strategies represent interesting and simple tools for the effective modulation of properties of star-shaped molecules.

Self-assembling supramolecular systems of different symmetry formed by wedged macromolecular dendrons

The main stages of the self-assembling of supramolecular ensembles have been revealed by studying different functional wedged macromolecules: polymethacrylates with tapered side chains based on gallic acid, their macromonomers, and salts of 2,3,4- and 3,4,5-tris(dodecyloxy)benzenesulphonic acid. The first stage is the formation of individual supramolecular aggregates (long cylinders or spherical micelles) due to the weak noncovalent interactions of mesogenic groups and the subsequent ordering in these aggregates, which is accompanied by a decrease in the free energy of the system. Supramolecular aggregates, in turn, form 2D or 3D lattices. The shape of supramolecular aggregates and its change with temperature are delicate functions of the mesogen chemical structure; this circumstance makes it possible to rationally design complex self-assembling systems with the ability to respond smartly to external stimuli. X-ray diffraction analysis allows one to study the structure of supramolecular systems with different degrees of order, determine the type of mesophases formed by these systems, and reveal the phase behavior of the material. Particular attention has been paid to the method for reconstruction of electron density distribution from the relative reflection intensity. The application of a suite of experimental methods, including wide- and small-angle X-ray diffraction, molecular modeling, differential scanning calorimetry, and polarization optical microscopy, allows one to establish the relationship between the shape of the structural unit (molecule or molecular aggregate), the nature of the interaction, and the phase behavior of the material.

Luminescent Organic Semiconducting Langmuir Monolayers

In recent years, monolayer organic field-effect devices such as transistors and sensors have demonstrated their high potential. In contrast, monolayer electroluminescent organic field-effect devices are still in their infancy. One of the key challenges here is to create an organic material that self-organizes in a monolayer and combines efficient charge transport with luminescence. Herein, we report a novel organosilicon derivative of oligothiophene-phenylene dimer D2-Und-PTTP-TMS (D2, tetramethyldisiloxane; Und, undecylenic spacer; P, 1,4-phenylene; T, 2,5-thiophene; TMS, trimethylsilyl) that meets these requirements. The self-assembled Langmuir monolayers of the dimer were investigated by steady-state and time-resolved photoluminescence spectroscopy, atomic force microscopy, X-ray reflectometry, and grazing-incidence X-ray diffraction, and their semiconducting properties were evaluated in organic field-effect transistors. We found that the best uniform, fully covered, highly ordered monolayers were semiconducting. Thus, the ordered two-dimensional (2D) packing of conjugated organic molecules in the semiconducting Langmuir monolayer is compatible with its high-yield luminescence, so that 2D molecular aggregation per se does not preclude highly luminescent properties. Our findings pave the way to the rational design of functional materials for monolayer organic light-emitting transistors and other optoelectronic devices.

Modern approaches to investigation of thin films and monolayers: X-ray reflectivity, grazing-incidence X-ray scattering and X-ray standing waves

The review concerns modern experimental methods of structure determination of thin films of different nature. The methods are based on total reflection of X-rays from the surface and include X-ray reflectivity, grazing-incidence X-ray scattering and X-ray standing waves. Their potential is exemplified by the investigations of various organic macromolecular systems that exhibit the properties of semiconductors and are thought to be promising as thin-film transistors, light-emitting diodes and photovoltaic cells. It is shown that combination of the title methods enable high-precision investigations of the structure of thin-film materials and structure formation in them, i.e., it is possible to obtain information necessary for improvement of the operating efficiency of elements of organic electronic devices. The bibliography includes 92 references.

Effect of low molecular additives on the electrospinning of nonwoven materials from a polyamide-6 melt

The effect of low molecular additives on the structure and properties of polyamide-6-based nonwoven materials obtained via electrospinning from a melt is studied. The introduction of up to 10% salts of higher fatty acids into the polymer melt leads to a decrease in its viscosity and to an increase in its electrical conductivity, thereby making it possible to produce nonwoven materials with an average fiber diameter of <1.5 µm. With the use of DSC, IR spectroscopy, and X-ray diffraction, it is shown that, in nonwoven materials based on polyamide-6, the metastable γ form of crystals prevails, while, in the native polymer, the stable a form predominates. The resulting materials demonstrate high filtration characteristics, and their surface properties are close to superhydrophobic.

Thiophene-based monolayer OFETs prepared by Langmuir techniques

A novel fast, easily processible and highly reproducible approach to thiophene-based monolayer OFETs fabrication by Langmuir-Blodgett or Langmuir-Schaefer techniques was developed and successfully applied. It is based on selfassembly of organosilicon derivatives of oligothiophenes or benzothienobenzothiophene on the water-air interface. Influence of the conjugation length and the anchor group chemistry of the self-assembling molecules on the monolayer structure and electric performance of monolayer OFETs was systematically investigated. The efficient monolayer OFETs with the charge carrier mobilities up to 0.01 cm2/Vs and on/off ratio up to 106 were fabricated, and their functionality in integrated circuits under normal air conditions was demonstrated.

Ion channel forming self-assembling systems based on benzenesulfonic acid with unsaturated aliphatic substituents

The structure and phase behavior of amphiphilic compound sodium 2,3,4-tri(dodecyl)benzenesulfonate, which is capable of self-assembling and contains methacryloyl groups in aliphatic ends, were studied by X-ray diffraction and differential scanning calorimetry. The initial samples are characterized by an ordered columnar ϕoh phase, which, during a rise in temperature to 53°C (at the expense of mobility, an increase in mesogenic groups, and a loss of order in their mutual arrangement), transforms into a disordered columnar ϕh phase. Under the action of irradiation, the cross-linking of benzenesulfonate molecules by methacryloyl groups and the formation of a continuous polymer matrix occur, which leads to a consistency of the column diameter at high temperatures. Cross linking proceeds much more intensively in the area where the disordered columnar phase exists. To analyze the structure of the columnar phase, we used an established technique: the reconstruction of electron density distribution maps in cylindrically symmetric systems from the relation of the intensities of small-angle X-ray reflections. Mutual ordering of benzenesulfonic groups in the area where the ϕoh phase exists leads to the formation of ordered ion channels; this opens up possibilities to use this material to make ion-selective membranes with controlled conductivity.