2,2′-Azobis­(5-azidotetrazole) (C2N16, 3), a highly energetic nitrogen-rich binary CN compound was obtained in a three-step synthesis through the formation of 5-azidotetrazole (1), subsequent amination using O-tosylhydroxylamine to give 2-amino-5-azidotetrazole (2), and oxidative azo coupling of 2 using tBuOCl as an oxidant in MeCN. A nitrogen:carbon ratio of 8:1, eight nitrogen atoms in a row, and a nitrogen content of over 90% was unknown for a binary heterocyclic compound until now. The successful isolation was confirmed through X-ray diffraction as well as by vibrational and 13C NMR spectroscopy. C2N16 can explode instantly and shows mechanical sensitivities far higher than quantitatively measurable. Nevertheless, it features interesting energetic performances, which were calculated using different quantum-chemical methods.

A mild cobalt-catalyzed Negishi-type cross-coupling of various functionalized dialkylzinc reagents with primary and secondary alkyl iodides in acetonitrile is reported using a combination of 20% CoCl 2 and chelating nitrogen ligands. The method allows the construction of molecules with alkyl chains bearing sensitive functional groups at room temperature.

Grimm–Sommerfeld analogous II‐IV‐N2 nitrides such as ZnSiN2, ZnGeN2, and MgGeN2 are promising semiconductor materials for substitution of commonly used (Al,Ga,In)N. Herein, the ammonothermal synthesis of solid solutions of II‐IV‐N2 compounds (II=Mg, Mn, Zn; IV=Si, Ge) having the general formula (IIa 1−xIIb x)‐IV‐N2 with x≈0.5 and ab initio DFT calculations of their electronic and optical properties are presented. The ammonothermal reactions were conducted in custom‐built, high‐temperature, high‐pressure autoclaves by using the corresponding elements as starting materials. NaNH2 and KNH2 act as ammonobasic mineralizers that increase the solubility of the reactants in supercritical ammonia. Temperatures between 870 and 1070 K and pressures up to 200 MPa were chosen as reaction conditions. All solid solutions crystallize in wurtzite‐type superstructures with space group Pna21 (no. 33), confirmed by powder XRD. The chemical compositions were analyzed by energy‐dispersive X‐ray spectroscopy. Diffuse reflectance spectroscopy was used for estimation of optical bandgaps of all compounds, which ranged from 2.6 to 3.5 eV (Ge compounds) and from 3.6 to 4.4 eV (Si compounds), and thus demonstrated bandgap tunability between the respective boundary phases. Experimental findings were corroborated by DFT calculations of the electronic structure of pseudorelaxed mixed‐occupancy structures by using the KKR+CPA approach.

The azotetrazole moiety represents a great platform for energetic materials, it offers a planar and nitrogen‐rich backbone, combined with a high heat of formation, which easily can be functionalized and tuned. Herein, we start from sodium 5‐aminotetrazolate and obtain two isomers by substitution reaction with 2‐chloroethanol. Azidoethyl and nitratoethyl substituted azo‐ tetrazoles were finally synthesized by oxidative azo coupling of the respective N‐ethyl functionalized 5‐aminotetrazole precursors using tert‐butyl hypochlorite as reagent. All compounds were analyzed through multicore NMR and IR spectroscopy as well as mass spectrometry. All solid compounds were further investigated using low‐temperature X‐ray crystallography. The purity was verified by CHNO elemental analysis and the decomposition temperature (DTA) and sensitivities toward impact, friction and electrostatic discharged were determined. Based on the CBS‐4M calculation results, the energetic properties were calculated using the EXPLO5 code.

Recently, different nitrato-methyl-substituted oxadiazoles have been described as potential melt-cast explosives. In this work, corresponding N–O heterocyclic-based compounds with azido-methyl functionalities were synthesized. In each case, the explosophoric azide group is inserted by chlorine–azide exchange during the last synthetic step. All synthesized compounds show interesting characteristics for various applications in the field of energetic materials as energetic plasticizers or as melt-cast explosives. The compounds were extensively analyzed by IR, EA DTA, and multinuclear NMR spectroscopy. Furthermore, the solid compounds 4,4′,5,5′-tetrakis­(azidomethyl)-3,3′-bisisoxazole (2) and 3,3′-bis­(azidomethyl)-5,5′-bis­(1,2,4-oxadiazole) (4) were characterized using X-ray diffraction. In addition, the sensitivities toward friction and impact were determined with BAM standard techniques, and the energetic performances of all synthesized azido-methyl compounds were calculated using the EXPLO5 code. The properties were compared to recently published, structurally related compounds.