A convenient synthesis of diaminoglyoxime and diaminofurazan: Useful precursors for the synthesis of high density energetic materials

The reaction of glyoxime ( 4 ) and hydroxylamine hydrochloride in aqueous sodium hydroxide was found to be a safe and inexpensive method for the preparation of multigram quantities of diaminoglyoxime ( 5 ). Potassium hydroxide mediated dehydration of 5 furnished diaminofurazan ( 1 ) in good yield of exceptional purity. The ready availability of 1 and 5 has facilitated the synthesis of new energetic furazan derivative 8 .     

Morphology and oxygen sensor response of luminescent Ir-labeled poly(dimethylsiloxane)/polystyrene polymer blend films

Polymer films consisting of a linear poly(dimethylsiloxane) end-functionalized with a luminescent Ir(III) complex (Ir-PDMS), blended with polystyrene (PS), function as optical oxygen sensors. The sensor response arises by quenching of the luminescence from the Ir(III) chromophore by oxygen that permeates into the polymer film. The morphology and luminescence oxygen sensor properties of blend films consisting of Ir-PDMS and PS have been characterized by fluorescence microscopy, atomic force microscopy, and scanning electron microscopy. The investigations demonstrate that microscale phase segregation occurs in the films. In blends that contain a relatively small amount of Ir-PDMS in PS (ca. 10 wt %), the Ir-PDMS exists as circular domains, with diameters ranging from 2 to 5 mum, surrounded by the majority PS phase. For larger weight fractions of Ir-PDMS in the blends, the film morphology becomes bicontinuous. A novel epifluorescence microscopy method is applied that allows the construction of Stern-Volmer quenching images that quantify the oxygen sensor response of the blend films with micrometer spatial resolution. These images provide a map of the oxygen permeability of the polymer blend films with a spatial resolution of ca. 1 mum. The results of this investigation show that the micrometer-sized Ir-PMDS domains display a 2-3-fold higher oxygen sensor response compared to the surrounding PS matrix. This result is consistent with the fact that PDMS is considerably more gas permeable compared to PS. The relationship of the microscale morphology of the blends to their performance as macroscale optical oxygen sensors is discussed.     

Use ofD J,DJK constants for the unique fixing of intramolecular forces inXY 3 pyramidal molecules

A mathematical formalism is developed to evaluate all the possible sets of intramolecular force fields fitting fundamental vibrational frequencies and centrifugal distortion constants in the case ofXY ₃ pyramidal type molecules. The method is applied to PF₃ molecule as an example. It is found that there exist as many as four sets of force field fitting all the above experimental data. A few general criteria are suggested to eliminate the suprious sets, thus making further experimental data unnecessary to fix the true physical force field.     

Paintable Room‐Temperature Phosphorescent Liquid Formulations of Alkylated Bromonaphthalimide

Organic phosphors have been widely explored with an understanding that crystalline molecular ordering is a requisite for enhanced intersystem crossing. In this context, we explored the room‐temperature phosphorescence features of a solvent‐free organic liquid phosphor in air. While alkyl chain substitution varied the physical states of the bromonaphthalimides, the phosphorescence remained unaltered for the solvent‐free liquid in air. As the first report, a solvent‐free liquid of a long swallow‐tailed bromonaphthalimide exhibits room‐temperature phosphorescence in air. Doping of the phosphor with carbonyl guests resulted in enhanced phosphorescence, and hence a large‐area paintable phosphorescent liquid composite with improved lifetime and quantum yield was developed.     

The determination of force constants from isotopic frequencies using parameter representation

The problem of fixing the molecular force field using isotopic frequencies is approached from a new angle with the help of the parameter technique. A parameter space is defined with the parameters for the molecule and its isotopic substituent as the coordinates. Making use of the constraint that the F elements are invariant under isotopic substitution in the ideal case, it is shown that unique points must exist in the parameter space enabling the determination of the force field. The method is applied to harmonic vibrations of molecules with 2 × 2 secular equations. The displays in the parameter space indicate that two such points exist for all molecules. Thus there can be two sets of force fields capable of reproducing the observed frequencies for the molecule and its isotopic substituents. Checks with mean amplitudes of vibration favour only one set. The calculated values of the force constants compare well with the values from the literature.