Synthesis,Structure, Molecular Orbital and Valence Bond Calculations for Tetrazole Azide,CHN7

The synthesis, NMR spectroscopic characterization and structure determination of highly explosive tetrazole azide, a very nitrogen‐rich material (88.3% N) is reported. Tetrazole azide was prepared in high yield from the diazotation reaction of aminotetrazole, followed by treatment of the formed diazonium salt with sodium azide. Synthesis in diethylether/methanol and recrystallization from diethylether afforded colorless cubes: CHN₇ ( 1 ): monoclinic, P1 2₁/n₁, a=1346.6(5), b=499.6(2), c=1360.9(5) pm, β=105.14(1)⁰, V=0.884(2) nm³, Z=8, ϱ=1.670 g cm⁻³. The observed structural parameters (X‐ray) are in good accordance with the results from molecular orbital (MO) calculations. The computed electrostatic potential (B3LYP) suggests a pronounced shock and friction sensitivity which was confirmed experimentally. Quantitative valence bond (VB) calculations were performed for the most important 21 VB structures in order to obtain the structural weights and to obtain an assessment for the importance of the various individual VB structures considered.     

新显色剂2,3,7-三羟基-9-(2,4-二羟基)苯基荧光酮的合成及与金属离子显色反应的研究

以对苯二酚，2，4－二羟基苯甲醛为基本原料，报道了新显色剂2，3，7－三羟基－9－（2，4－二羟基）苯基荧光酮（DHPF）的合成方法。通过对试剂进行红外光谱、紫外光谱、元素分析确证了试剂的结构。采用分光光度法测定了试剂在水溶液中的离解常数。在表面活性剂存在下研究了试剂与一些高价金属离子的显色反应特性。     

Molecular Dynamics Study of Complex Dopant Electrolyte Nd2–xHoxZr2O7: Structure,Conductivity, and Thermal Expansion

Nd_2–xHo_xZr₂O₇ is an ionic conductor for solid oxide fuel cell electrolytes. Temperature and dopant composition are two main factors that affect ionic conductivity of these groups of materials. Accordingly, Nd_2–xHo_xZr₂O₇ was studied in a wide range of temperature, 1,173–1,873 K, and dopant composition, x = 0.0–2.0, by molecular dynamics simulation. Arrhenius plots of ionic conductivity in region of low temperature declared that the maximum occurred at composition x = 0.6 (H6). Surprisingly, it was observed that complexity of dopant improved ionic conductivity of the electrolyte. Moreover, radial distribution function confirmed this result. Two types of anions were observed in the electrolyte, which were dynamic oxygen ions (DOIs) and static oxygen ions (SOIs). Mean square displacement (MSD) of DOIs was higher than SOIs and enhanced oxygen ionic conductivity. Migration barrier of Nd_2–xHo_xZr₂O₇ varied from 0.68 to 1.22 eV that was in the range of a good solid oxide electrolyte. Nd_1.2Gd_0.8Zr₂O₇ (G8) and Y_0.2Zr_0.9O_2.1 (Y2) were simulated and their results of simulations were compared with H6. Order of ionic conductivity at low temperatures was H6 > Y2 > G8. Another important factor of electrolyte is thermal expansion. Thermal expansion of Nd_2–xHo_xZr₂O₇ was around a constant value in the studied temperature range.     

Molecular Structure,Vibrational Spectrum and Conformational Properties of 4-(4-Tritylphenoxy)phthalonitrile-Precursor for Synthesis of Phthalocyanines with Bulky Substituent

By DFT method with B3LYP, PBE, CAM-B3LYP, and B97D functionals, it was found that the molecule 4-(4-tritylphenoxy)phthalonitrile (TPPN) has four conformers. The geometric structure, vibrational frequencies, electronic characteristics, and thermodynamic functions of conformers, as well as the structure and energy of transition states, were determined. IR spectrum of TPPN film contains vibrational bands belonging to different conformers. The assignment of bands was performed basing the distribution of normal vibration energy on internal coordinates. A synchronous electron diffraction/mass spectrometric experiment was performed to determine the structure of conformers in a saturated TPPN vapor. The elemental composition of the ions recorded in the mass spectrum indicates the thermal stability of TPPN at least up to T = 200 °C. The difference in the structure of tetrasubstituted metal phthalocyanines, which can be synthesized from different TPPN conformers, has been shown.