Self-Phosphorylated Polybenzimidazole: An Environmentally Friendly and Economical Approach for Hydrogen/Air High-Temperature Polymer-Electrolyte Membrane Fuel Cells.

The development of phosphorylated polybenzimidazoles (PBI) for high-temperature polymer-electrolyte membrane (HT-PEM) fuel cells is a challenge and can lead to a significant increase in the efficiency and long-term operability of fuel cells of this type. In this work, high molecular weight film-forming pre-polymers based on N1,N5-bis(3-methoxyphenyl)-1,2,4,5-benzenetetramine and [1,1'-biphenyl]-4,4'-dicarbonyl dichloride were obtained by polyamidation at room temperature for the first time. During thermal cyclization at 330-370 °C, such polyamides form N-methoxyphenyl substituted polybenzimidazoles for use as a proton-conducting membrane after doping by phosphoric acid for H2/air HT-PEM fuel cells. During operation in a membrane electrode assembly at 160-180 °C, PBI self-phosphorylation occurs due to the substitution of methoxy-groups. As a result, proton conductivity increases sharply, reaching 100 mS/cm. At the same time, the current-voltage characteristics of the fuel cell significantly exceed the power indicators of the commercial BASF Celtec® P1000 MEA. The achieved peak power is 680 mW/cm2 at 180 °C. The developed approach to the creation of effective self-phosphorylating PBI membranes can significantly reduce their cost and ensure the environmental friendliness of their production.

New Titanium(IV)-Alkoxide Complexes Bearing Bidentate OO Ligand with the Camphyl Linker as Catalysts for High-Temperature Ethylene Polymerization and Ethylene/1-Octene Copolymerization.

In order to increase the thermal stability of olefin polymerization precatalysts, new titanium(IV) complexes with diolate ligands differing in the degree of steric hindrances were synthesized from readily available precursor (±)camphor. The structures of the complexes 1-2 were established by X-ray diffraction. Complexes 1-4 in the presence of an activator {EtnAlCl3-n + Bu2Mg} catalyzed the synthesis of UHMWPE with an Mv up to 10 million and a productivity of up to 3300 kg/molTi·atm·h. The obtained polymers are obviously characterized by a low density of macromolecular entanglement, which makes it possible to use the solid-phase method for their processing. The mechanical characteristics of the oriented UHMWPE films had a breaking strength up to 2.7 GPa and an elastic modulus of up to 151 GPa. The precatalysts 1-4 were also active in ethylene/1-octene copolymerization. The comonomer content was in the range of 1.4-4.6 mol%. The use of a rigid linker and an increase in the steric load of the diolate complexes ensured the thermal stability of the catalytic system in the range of 50-70 °C.

Effect of Activator and Outgoing Ligand Nature on the Catalytic Behavior of Bis(phenoxy-imine) Ti(IV) Complexes in the Polymerization of Ethylene and Its Copolymerization with Higher Olefins.

A series of bis(phenoxy-imine) (FI) titanium(IV) and zirconium(IV) complexes have been synthesized. The effect of the nature of the activator (MAO, combinations EtnAlCl3-n + Bu2Mg and iBu3Al + [Ph3C]+[B(C6F5)4]-) on the catalytic activity and properties of the resulting polymers was studied. It was found that Ti-Fi complexes, despite the nature of the outgoing ligands (Cl or iPrO) in the presence of Al/Mg activators, effectively catalyze the polymerization of ethylene (with the formation of UHMWPE); copolymerization of ethylene with 1-octene (with the formation of ultra-high molecular weight copolymers); and the ternary copolymerization of ethylene, propylene and 5-vinyl-2-norbornene (with the formation of polyolefin elastomers). It has been shown that Zr-FI complexes are not activated by these Al/Mg compositions. The resulting UHMWPE can be processed by a solventless method into high-strength and high-modulus oriented films; however, their mechanical characteristics do not exceed those obtained using MAO.

Star-Shaped Polydimethylsiloxanes with Organocyclotetrasilsesquioxane Branching-Out Centers: Synthesis and Properties.

New non-crystallizable low-dispersity star-shaped polydimethylsiloxanes (PDMS) containing stereoregular cis-tetra(organo)(dimethylsiloxy)cyclotetrasiloxanes containing methyl-, tolyl- and phenyl-substituents at silicon atoms and the mixture of four stereoisomers of tetra[phenyl(dimethylsiloxy)]cyclotetrasiloxane as the cores were synthesized. Their thermal and viscous properties were studied. All synthesized compounds were characterized by a complex of physicochemical analysis methods: nuclear magnetic resonance (NMR), FT-IR spectroscopy, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), viscometry in solution, rheometry, and Langmuir trough study.

A Versatile Equilibrium Method for the Synthesis of High-Strength, Ladder-like Polyphenylsilsesquioxanes with Finely Tunable Molecular Parameters.

A versatile equilibrium method for synthesizing ladder-like polyphenylsilsesquioxanes (L-PPSQs) with various molecular weights (from 4 to 500 kDa) in liquid ammonia was developed. The effect of diverse parameters, such as temperature, monomer concentration, reaction time, addition or removal of water from the reaction medium, on the polycondensation process was determined. The molecular weight characteristics and structure of the L-PPSQ elements obtained were determined by GPC, 1H, 29Si NMR, IR spectroscopy, viscometry, and PXRD methods. The physicochemical properties of L-PPSQs were determined by TGA and mechanical analyses.

Multiarm Star-Shaped Polydimethylsiloxanes with a Dendritic Branching Center.

New multiarm stars have been synthesized based on polylithium derivatives of high-generation carbosilane dendrimers. In the synthesis of multiarm stars based on the eighth-generation dendrimer, steric hindrances were observed even during the synthesis of a polylithium initiator. Subsequently, this led to chain transfer reactions between growing arms, as well as other side effects. As a result, dense nanogel formations with a higher tendency of ordering than in classical objects of this type were isolated from the reaction mixture. The study of the rheology of multiarm stars based on sixth-generation dendrimers made it possible to determine the activation energies of viscous flow in these objects, which makes it possible to consider them as objects with a macromolecular nature and a reptation flow mechanism.

Solid-state 1D → 3D transformation of polynitrile-based coordination polymers by dehydration reaction.

In crystal structures of two chain coordination polymers [M(tcnopr3OH)2(H2O)2] (M = NiII and CoII; tcnopr3OH- = [(NC)2CC(O(CH2)3OH)C(CN)2]-) based on a N,O or N,N'-bridge polynitrile ligand, the parallel chains are connected via, respectively, C[triple bond, length as m-dash]NH-O and O-HO hydrogen bonds between uncoordinated functional groups of the ligand and coordinated water molecules. Upon heating, both solids undergo dehydration accompanied by degradation of their single crystals. Powder X-ray diffraction showed that non-isostructural triclinic single crystals transformed to isostructural monoclinic compounds. The solid-state reaction yielded 3D coordination polymers [M(tcnopr3OH)2] (M = NiII and CoII) based on a N,N',O-connected tcnopr3OH-. Although previously tens of complexes based on tcnopr3OH and similar anions were synthesized and X-ray characterized, none of these contain a tridentate polynitrile ligand. Thus, this study provides evidence that solid-state reactions allow obtaining novel coordination modes of polynitrile ligands. The possible pathways for the transformation of H-bonded networks to 3D coordination polymers are discussed on the basis of the topological approach. Applicability of the topological approach to predict possible networks of solid-state reaction products based on the crystal structures of initial compounds is demonstrated.

A Novel Ziegler⁻Natta-Type Catalytic System-TiCl4/2,2'-Dimethoxy-1,1'-Binaphthalene/Et3Al2Cl3/Bu2Mg for Production of Ultrahigh Molecular Weight Polyethylene Nascent Reactor Powders, Suitable for Solvent-Free Processing.

A series of ultrahigh molecular weight polyethylenes with viscosity-average molecular weights in the range of 1.6⁻5.6 × 106 have been prepared by using a novel Ziegler⁻Natta-type catalytic system-TiCl4/2,2'-dimethoxy-1,1'-binaphthalene/Et3Al2Cl3/Bu2Mg at different temperatures (Tpoly) in the range between 10 and 70 °C in toluene. The morphology of the nascent reactor powders has been studied by scanning electron microscopy, wide-angle X-ray diffraction, and the DSC melting behavior. Polymers are suitable for the modern processing methods-the solvent-free solid-state formation of super high-strength (tensile strength over 1.8⁻2.5 GPa) and high-modulus (elastic modulus up to 136 GPa) oriented film tapes. With decrease of Tpoly, the drawability of the reactor powders increased significantly.

Solid-State Reactions of Eicosaborate [B20 H18 ]2- Salts and Complexes.

A series of salts and complexes containing trans- and iso-isomers of octadecahydro-eicosaborate [B20 H18 ]2- dianion is synthesized and characterized using FTIR and 11 B NMR spectroscopies and X-ray diffraction techniques. Both isomers are found to act as four-, bi-, or zero-dentate ligands in reactions with copper(II), silver(I), and lead(II) through apical and/or equatorial boron atoms. Solid-state photo- and thermoinitiated reactions of octadecahydro-eicosaborate isomerization and solvent cleavage occurring in these compounds in a single-crystal-to-single-crystal manner are studied in situ. In contrast with solutions, in solids the reaction of boron cluster transformation occurs rarely, thus, analysis of crystal packing allowed us to suggest some criteria of isomerization of macropolyhedral boranes in crystals. X-ray diffraction data are used to confirm reaction path of isomerization of the [B20 H18 ]2- dianion.

Triphenylamine-Based Push-Pull Molecule for Photovoltaic Applications: From Synthesis to Ultrafast Device Photophysics.

Small push-pull molecules attract much attention as prospective donor materials for organic solar cells (OSCs). By chemical engineering, it is possible to combine a number of attractive properties such as broad absorption, efficient charge separation, and vacuum and solution processabilities in a single molecule. Here we report the synthesis and early time photophysics of such a molecule, TPA-2T-DCV-Me, based on the triphenylamine (TPA) donor core and dicyanovinyl (DCV) acceptor end group connected by a thiophene bridge. Using time-resolved photoinduced absorption and photoluminescence, we demonstrate that in blends with [70]PCBM the molecule works both as an electron donor and hole acceptor, thereby allowing for two independent channels of charge generation. The charge-generation process is followed by the recombination of interfacial charge transfer states that takes place on the subnanosecond time scale as revealed by time-resolved photoluminescence and nongeminate recombination as follows from the OSC performance. Our findings demonstrate the potential of TPA-DCV-based molecules as donor materials for both solution-processed and vacuum-deposited OSCs.

Titanium(III, IV)-Containing Catalytic Systems for Production of Ultrahigh Molecular Weight Polyethylene Nascent Reactor Powders, Suitable for Solventless Processing-Impact of Oxidation States of Transition Metal.

Catalytic systems containing TiCl4 or TiCl3, THF, organomagnesium (n-Bu2Mg) and organoaluminum compounds capable of producing ultrahigh molecular weight polyethylene (UHMWPE) were developed. The resulting polymers were characterized by a molecular weight in the range of (1.8⁻7.8) × 106 Da and desirable morphology, suitable for modern methods of polymer processing-the solvent-free solid-state processing of superhigh-strength (tensile strength up to 2.1 GPa) and high-modulus (elastic modulus up to 125 GPa) oriented films and film tapes. The impacts of a THF additive, the oxidation state of the titanium atom, and the composition and nature of the nontransition organometallic compounds on the formation of catalytic systems for UHMWPE production were evaluated. The results indicate the suitability of individual titanium chloride tetrahydrofuran complex application for the formation of THF-containing catalytic systems. This approach also results in a significant increase in the system catalytic activity and mechanical properties of UHMWPE. The catalysts based on Ti(III) were inferior to systems containing Ti(IV) in productivity but were markedly superior in the mechanical properties of UHMWPE.

A New Volume-Based Approach for Predicting Thermophysical Behavior of Ionic Liquids and Ionic Liquid Crystals.

Volume-based prediction of melting points and other properties of ionic liquids (ILs) relies on empirical relations with volumes of ions in these low-melting organic salts. Here we report an accurate way to ionic volumes by Bader's partitioning of electron densities from X-ray diffraction obtained via a simple database approach. For a series of 1-tetradecyl-3-methylimidazolium salts, the volumes of different anions are found to correlate linearly with melting points; larger anions giving lower-melting ILs. The volume-based concept is transferred to ionic liquid crystals (ILs that adopt liquid crystalline mesophases, ILCs) for predicting the domain of their existence from the knowledge of their constituents. For 1-alkyl-3-methylimidazolium ILCs, linear correlations of ionic volumes with the occurrence of LC mesophase and its stability are revealed, thus paving the way to rational design of ILCs by combining suitably sized ions.

Stabilization of 1T-MoS2 Sheets by Imidazolium Molecules in Self-Assembling Hetero-layered Nanocrystals.

We report a facile, room-temperature assembly of MoS2-based hetero-layered nanocrystals (NCs) containing embedded monolayers of imidazolium (Im), 1-butyl-3-methylimidazolium (BuMeIm), 2-phenylimidazolium, and 2-methylbenzimidazolium molecules. The NCs are readily formed in water solutions by self-organization of the negatively charged, chemically exfoliated 0.6 nm thick MoS2 sheets and corresponding cationic imidazole moieties. As evidenced by transmission electron microscopy, the obtained NCs are anisotropic in shape, with thickness varying in the range 5-20 nm and lateral dimensions of hundreds of nanometers. The NCs exhibit almost turbostratic stacking of the MoS2 sheets, though the local order is preserved in the orientation of the imidazolium molecules with respect to the sulfide sheets. The atomic structure of NCs with BuMeIm molecules was solved from powder X-ray diffraction data assisted by density functional theory calculations. The performed studies evidenced that the MoS2 sheets of the NCs are of the nonconventional 1T-MoS2 (metallically conducting) structure. The sheets' puckered outer surface is formed by the S atoms and the positioning of the BuMeIm molecules follows the sheet nanorelief. According to thermal analysis data, the presence of the BuMeIm cations significantly increases the stability of the 1T-MoS2 modification and raises the temperature for its transition to the conventional 2H-MoS2 (semiconductive) counterpart by ∼70 °C as compared to pure 1T-MoS2 (∼100 °C). The stabilizing interaction energy between inorganic and organic layers was estimated as 21.7 kcal/mol from the calculated electron density distribution. The results suggest a potential for the design of few-layer electronic devices exploiting the charge transport properties of monolayer thin MoS2.

Synthesis and Temperature-Induced Structural Phase and Spin Transitions in Hexadecylboron-Capped Cobalt(II) Hexachloroclathrochelate and Its Diamagnetic Iron(II)-Encapsulating Analogue.

Template condensation of dichloroglyoxime with n-hexadecylboronic acid on the corresponding metal ion as a matrix under vigorous reaction conditions afforded n-hexadecylboron-capped iron and cobalt(II) hexachloroclathrochelates. The complexes obtained were characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV-vis, (1)H and (13)C{(1)H} NMR, (57)Fe Mössbauer spectroscopies, SQUID magnetometry, electron paramagnetic resonance, and cyclic voltammetry (CV) and by X-ray crystallography. The multitemperature single-crystal X-ray diffraction, SQUID magnetometry, and differential scanning calorimetry experiments were performed to study the temperature-induced spin-crossover [for the paramagnetic cobalt(II) complex] and the crystal-to-crystal phase transitions (for both of these clathrochelates) in the solid state. Analysis of their crystal packing using the molecular Voronoi polyhedra and the Hirshfeld surfaces reveals the structural rearrangements of the apical long-chain alkyl substituents resulting from such phase transitions being more pronounced for a macrobicyclic cobalt(II) complex. Its fine-crystalline sample undergoes the gradual and fully reversible spin transition centered at approximately 225 K. The density functional theory calculated parameters for an isolated molecule of this cobalt(II) hexachloroclathrochelate in its low- and high-spin states were found to be in excellent agreement with the experimental data and allowed to localize the spin density within a macrobicyclic framework. CV of the cobalt(II) complex in the cathodic range contains one reversible wave assigned to the Co(2+/+) redox couple with the reduced anionic cobalt(I)-containing species stabilized by the electronic effect of six strong electron-withdrawing chlorine substituents. The quasireversible character of the Fe(2+/+) wave suggests that the anionic iron(I)-containing macrobicyclic species undergo substantial structural changes and side chemical reactions after such metal-centered reduction.

Highly flexible molecule "Chameleon": reversible thermochromism and phase transitions in solid copper(II) diiminate Cu[CF3-C(NH)-CF═C(NH)-CF3]2.

Three thermochromic phases (α, green; ß, red; γ, yellow) and six polymorphic modifications (α(1), monoclinic, P2(1)/n, Z = 2; ß(1), monoclinic, P2(1)/c, Z = 4; ß(2), triclinic, P1[overline], Z = 4; ß(3), monoclinic, P2(1)/n, Z = 4; γ(1) and γ(2), tetragonal, P4(2)/n, Z = 4) have been found and structurally characterized for copper(II) diiminate Cu[CF(3)-C(NH)-CF═C(NH)-CF(3)](2) (1). The α phase is stable under normal conditions, whereas the high-temperature ß and γ phases are metastable at room temperature and transform slowly into the more stable α phase over several days or even weeks. X-ray diffraction study revealed that the title molecules adopt different conformations in the α, ß, and γ phases, namely, staircase-like, twisted, and planar, respectively. The investigation of the α, ß, and γ phases by differential scanning calorimetry showed that the three endothermic peaks in the range 283, 360, and 438 K are present on their thermograms upon heating/cooling. The two peaks at 283 and 360 K correspond to the solid-solid phase transitions, and the high-temperature peak at 438 K belongs to the melting process of 1. The temperature and thermal effect of all the observed transitions depend on the prehistory of the crystalline sample obtained. A reversible thermochromic single-crystal-to-single-crystal α(1)<--> ß(1) phase transition occurring within a temperature interval of 353-358 K can be directly observed using a CCD video camera of the X-ray diffractometer. A series of other solid-solid α(1)→γ(1), ß(2)→γ(1), ß(3)→γ(1), and γ(1)<-->γ(2) phase transitions can be triggered in 1 by temperature. It has been suggested that, under equilibrium conditions, the α(1)→γ(1) and ß(2)→γ(1) phase transitions should proceed stepwise through the α(1)→ß(1)→ß(2)→ß(3)→γ(1) and ß(2)→ß(3)→γ(1) stages, respectively. The mechanism of the phase transitions is discussed on the basis of experimental and theoretical data.

Tris-cis-tris-trans-dodeca[organo(dimethylorganosiloxy)]cyclododecasiloxanes {RSi(O)[OSiMe2R']}12. Self-ordering features.

The molecular order and thermotropic transitions of tris-cis-tris-trans-dodeca- [organo(dimethylorganosiloxy)]cyclododecasiloxanes {RSi(O)[OSiMe(2)R']}(12) (R = Ph, R' = Me, CH(2)Cl, Vi; R = Me, Et, Vi, R' = Me) have been investigated using differential scanning calorimetry, thermogravimetric analysis, and X-ray scattering. The cyclododecasiloxanes with phenyl side groups (R = Ph) can form mesomorphic structures within a very wide temperature range. Compounds with R = Me and Vi are liquids and exhibit microphase separation above their glass transition temperature because of the different nature and structure of the organic R and trimethylsiloxy OSiMe(3) side groups. When the side group R = Et, a mesomorphic structure is formed in a substantially more narrow temperature region than that for cycles containing phenyl groups. Thus, the type of side group R in organocyclododecasiloxanes determines their ability for self-ordering into mesomorphic structures and the thermal stability of the mesomorphic state.