Mixed Boron(III) and Phosphorous(V) Complexes of meso‐Triaryl 25‐Oxasmaragdyrins

Two unprecedented mixed B^III/P^V complexes of meso‐triaryl 25‐oxasmaragdyrins were synthesized in appreciable yields under mild reaction conditions. These unusual 25‐oxasmaragdyrin complexes containing one or two seven‐membered heterocyclic rings comprised of five different atoms (B, C, N, O, and P) were prepared by reacting B(OH)(Ph)‐smaragdyrin and B(OH)₂‐smaragdyrin complexes, respectively, with POCl₃ in toluene at reflux temperature. The products were characterized by HRMS and 1D‐ and 2D‐NMR spectroscopy. X‐ray crystallography of one of the mixed B^III/P^V smaragdyrin complexes indicated that the macrocycle is significantly distorted and contains a stable seven‐membered heterocyclic ring within the macrocycle. The bands in the absorption and emission spectra were bathochromically shifted with reduced quantum yields and singlet‐state lifetimes relative to the free base, meso‐triaryl 25‐oxasmaragdyrin. The mixed B^III/P^V complexes were difficult to oxidize but easier to reduce than the free base. The DFT‐optimized structure of the 25‐oxasmaragdyrin complex with two seven‐membered heterocycles indicated that it was a bicyclic spiro compound with two half‐chair‐like conformers. This was in contrast to the chair‐like conformation of the complex with a single seven‐membered heterocyclic ring. Moreover, incorporation of a second phosphate group in the former case stabilized the bonding geometry and resulted in higher stability, which was reflected in the bathochromic shift of the absorption spectra, more‐positive oxidation potential, and less‐negative reduction potential.     

Theory of the transition from conductive to convective burning

The experimentally known phenomenon of an abrupt transition from slow conductive to fast convective (penetrative) burning in a confined gas-permeable explosive is discussed. A simple model, involving only the most essential physical ingredients, is formulated and analyzed. A good qualitative agreement between theoretical and experimental dependencies is obtained. The transition is triggered by a localized autoignition in the extended resistance-induced preheat zone formed ahead of the advancing deflagration, provided the pressure difference between hot gas products and gases deep inside the pores of the unburned solid exceeds a certain critical level. In line with observations the critical overpressure increases with diminishing permeability.     

Polynitro-Functionalized Dipyrazolo-1,3,5-triazinanes: Energetic Polycyclization toward High Density and Excellent Molecular Stability

A new fused N-heterocyclic framework, dipyrazolo-1,3,5-triazinane, was synthesized and the physiochemical properties of its derivatives were investigated to evaluate the integrated energetic performance. In contrast to 1,3,5-trinitro-1,3,5-triazinane (RDX) featuring a distorted chair confirmation, polynitro-functionalized dipyrazolo-1,3,5-triazinanes have nearly planar backbones, thereby enhancing the density and thermal stability. Among these new energetic tricyclic compounds, 5 a and 12 show favorable crystal densities of 1.937 g cm⁻³ and 1.990 g cm⁻³ at 150 K, respectively, which rank highest in triazinane-based energetic compounds. Additionally, this synthetic approach was carried out to form seven-membered and eight-membered rings, giving rise to tetranitro dipyrazolo-1,3,5-triazepane ( 5 b ) and tetranitro dipyrazolo-1,3,5-triazocane ( 5 c ), respectively.     

2-Butyl-4-iodoimidazole-5-carboxaldehyde: A Versatile Intermediate for the Synthesis of Highly Functionalized Imidazoles

The facile preparation of 2-butyl-4-iodoimidazole-5-carboxaldehyde 1 is described. The versatility of this intermediate in the synthesis of highly tunctionalized imidazoles is demonstrated with the synthesis of two potent and selective angiotensin II receptor antagonists.     

Novel,highly polarizable thiophene derivatives for use in nonlinear optical applications

The synthesis of a variety of thiophene-containing materials for use in electro-optic devices requiring highly birefringent materials is reported. The refractive indices were measured with the use of an Abbé refractometer, and from these results the optical anisotropies, polarizabilities and order parameters were determined. The replacement of a phenyl ring by thiophene leads to large enhancements of polarizability. The most significant increases in polarizability anisotropy were observed when the rigid core was a collinear 5,5′-disubstituted-2,2′-dithienyl unit. The changes in the optical properties are discussed in terms of the structural units (thiophene, phenyl, isothiocyanate, nitrile, butylsulfanyl, alkoxy and alkyl moieties) used and their positions with respect to the molecular core.     

X‐ray photoelectron spectroscopy process optimization for characterization of trace contamination elements for extreme ultraviolet resist outgassing study

X‐ray photoelectron spectroscopy (XPS) is used for elemental identification and quantification in a number of fields, and the optimization of XPS performance can help in making better use of the limited XPS tool availability. In the field of extreme ultraviolet (EUV) lithography, one of the requirements is having a clean vacuum environment to minimize contamination of the EUV optics. EUV resist outgassing is viewed as one of the main issues that could affect the vacuum environment. There is a program underway to measure the relative contamination rates from different resists following the ASML (provider of lithography systems) approved protocols for witness plate testing. One of the key steps is the XPS measurement of residue on the optics after cleaning. The role of XPS in quantification of species that adhere to the ruthenium‐coated silicon witness plate sample is discussed. The various XPS tool parameters like the pass energy and source setting were optimized for our application of witness plate analysis. The statistics of our XPS tool were studied, and combined with the fundamental XPS equations, a simple mathematical model was developed to optimize the number of scans for the various elements of interest in our witness plate study. Using the optimized number of scans, the acquisition time to measure the contaminant elements to a precision better than 0.1 at.% was minimized. The model devised in the paper can be adapted to other XPS measurements requiring different levels of precision. Copyright © 2013 John Wiley & Sons, Ltd.     

Control of modulated vibration using an enhanced adaptive filtering algorithm based on model-based approach

Conventional adaptive filtering algorithms, typically limited to the control of single or multiple sinusoids, are not appropriate to control modulated vibrations, especially in the presence of rich side band structures. To overcome this deficiency, a new control algorithm is proposed that introduces a feedback loop with the model predictive sliding mode control (MPSMC) in the adaptive filtering system. Several amplitude and frequency modulation cases are first computationally studied, and conventional and proposed methods are comparatively evaluated in terms of estimation error, performance in time and frequency domains, stability, and uncertainty in the reference signal. To experimentally validate the proposed algorithm, an active strut (with longitudinal vibrations) is constructed. Overall, the proposed adaptive algorithm yields superior reductions at the main frequencies and at side bands; also, good attenuation is found on a broadband basis.