• Mcgowan Whitaker posted an update 6 days, 11 hours ago

    Herein, we describe the synthesis of tetraphenylphosphonium o-carboranyl dithiocarboxylate (Ligand 1) and methyldithiocarboxyl-o-carborane (Ligand 2). The complexes [Cp*M(o-C2B10H11CS2)Cl] (M = Ir (3); Rh (4)) and [Cp*M(o-C2B10H11CS2)2] (M = Ir (5); Rh (6)) have been synthesized based on Ligand 1. The selective B-H bond activation of Ligand 2 has also been explored, leading to the synthesis of the B-H activated complex [Cp*Ir(o-C2B10H10CS2CH3)Cl] (7) and four of its substituted derivatives (8, 9, 10 and 11). All of these compounds have been characterised through single-crystal X-ray diffraction, NMR, IR spectroscopy and elemental analysis.Thin film metal-insulator-metal capacitors with undoped hafnium oxide and a mixture of hafnium and zirconium oxides are prepared by sputtering from ceramic targets. The influence of the oxygen concentration while sputtering and of the zirconium concentration on the ferroelectric properties is characterized by electrical and structural methods. Depending on the ambient oxygen, the thin undoped hafnium oxide films show distinct ferroelectric properties. The interplay of oxygen and zirconia could improve the ferroelectric properties. By varying the ambient oxygen and zirconia concentration in the films, stabilization of the tetragonal, orthorhombic or monoclinic phase is possible. This phase stabilization is strongly influenced by the pre-existing phase and size of the nanocrystallites in the as-deposited films. In conclusion, the impact of the film stress coming from oxygen vacancies and oxygen interstitials is correlated with the phase and ferroelectric properties.α-Diketones are an important class of building blocks employed in many organic synthetic reactions. However, their coordination chemistry has rarely been explored. In light of this, our earlier report on [(acac)2RuII(μ-2,2′-pyridil)RuII(acac)2] (acac = acetylacetonate) showcased the sensitivity of a diketone fragment towards oxidative C-C cleavage. Following the lead, the synthesis of similar but stable diketo fragments containing diruthenium compounds was attempted. selleck chemical Three diruthenium compounds with the bridge 1,2-bis(2-hydroxyphenyl)ethane-1,2-dione (L) were prepared diastereomeric [(acac)2RuIII(μ-L2-)RuIII(acac)2], 1a(rac)/1b(meso), [(bpy)2RuII(μ-L2-)RuII(bpy)2](ClO4)2, [2](ClO4)2 and [(pap)2RuII(μ-L2-)RuII(pap)2](ClO4)2, [3](ClO4)2 with ancillary ligands of different donating/accepting characteristics. The metal is stabilised in different oxidation states in these complexes Ru(iii) is preferred in 1a/1b when σ-donating acac is used as the co-ligand whereas electron rich Ru(ii) is preferred in [2](ClO4)2 and [3](ClO4)2 when co-ligands of moderate to strong π-accepting properties are employed. The oxidative chemistry of these systems is of particular interest with respect to the participation of varying bridging-ligands which contain phenoxide groups. On the other hand, the reduction processes primarily resulting from the metal or the ancillary ligands are noteworthy as the normally reducible 1,2-diketo- group remains unreduced. These results have been rationalised and outlined from thorough experimental and theoretical investigations. The results presented here shed light on the stability of metal coordinated α-diketones as a function of their substituents.Polymer nanocomposites containing nanoscale fillers are an important class of materials due to their ability to access a wide variety of properties as a function of their composition. In order to take full advantage of these properties, it is critical to control the distribution of nanofillers within the parent polymer matrix, as this structural organization affects how the two constituent components interact with one another. In particular, new methods for generating ordered arrays of nanofillers represent a key underexplored research area, as emergent properties arising from nanoscale ordering can be used to introduce novel functionality currently inaccessible in random composites. The knowledge gained from developing such methods will provide important insight into the thermodynamics and kinetics associated with nanomaterial and polymer assembly. These insights will not only benefit researchers working on new composite materials, but will also deepen our understanding of soft matter systems in general. In this review, we summarize contemporary research efforts in manipulating nanofiller organization in polymer nanocomposites and highlight future challenges and opportunities for constructing ordered nanocomposite materials.Phase separated macromolecules play essential roles in many biological and synthetic systems. Physical characterization of these systems can be challenging because of limited sample volumes, particularly for phase-separated proteins. Here, we demonstrate that a classic method for measuring the surface tension of liquid droplets, based on the analysis of the shape of a sessile droplet, can be effectively scaled down to measure the interfacial tension between a macromolecule-rich droplet phase and its co-existing macromolecule-poor continuous phase. The connection between droplet shape and surface tension relies on the density difference between the droplet and its surroundings. This can be determined with small sample volumes in the same setup by measuring the droplet sedimentation velocity. An interactive MATLAB script for extracting the capillary length from a droplet image is included in the ESI.In the present paper, a new type of micro-mechanically motivated chain network model for rubber-like materials is proposed. The model captures topological constraints of polymer network chains, in particular, entanglements. The model demonstrates how the local molecular packing constraints modify under deformation and shows the impact of these changes on the macroscopic elasticity of the material. To this end, we combine concepts of a confining tube and a slip-link (reptation) model. In these models, entanglements of polymer chains play an important role. The nature of entanglements is discussed, and relationships governing entanglements are formulated in terms of molecular physics. In the context of nonlinear elasticity, we apply a non-affine concept which captures the liquid-like behavior of polymer networks at smaller scales in a more realistic way. Model predictions show good agreement with experimental results from uniaxial and biaxial tension tests.