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Polynitrogen and Nitrogen-Oxygen Molecular Systems: Synthesis, Reactivity and Application

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A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Physical Chemistry and Chemical Physics".

Deadline for manuscript submissions: closed (31 December 2022) | Viewed by 21490

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Special Issue Editor

Prof. Dr. Leonid Fershtat

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Guest Editor

N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences 47 Leninsky Prosp., 119991 Moscow, Russia
Interests: nitrogen heterocycles; organic materials; high-energy materials; pharmacologically active compounds; nitric oxide donors; organic synthesis
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Polyheteroatom molecular systems are of paramount importance for the preparation of novel organic and metal–organic functional materials and pharmacologically active substances. In this sense, the synthesis and reactivity of various polyheteroatom heterocycles enriched with nitrogen and oxygen atoms have received special research attention. In addition, structurally diverse acyclic polyheteroatom compounds (e.g., azides and nitro compounds) are considered to be useful precursors for the construction of valuable heterocycles or may serve as standalone organic ligands, components of organic functional and/or energetic materials, or be relevant in medicinal chemistry. This Special Issue plans to provide an overview of the most recent advances in the synthesis and reactivity of polynitrogen and nitrogen–oxygen molecular systems and their applications in diverse areas.

Potential topics include, but are not limited to:

the synthesis and reactivity of polynitrogen and nitrogen–oxygen heterocycles;
organic azides and click reactions; nitro compounds;
mesoionic and zwitter-ionic compounds;
polynitrogen and nitrogen–oxygen organic ligands;
organic and metal–organic functional materials;
pharmacologically active substances.

Prof. Dr. Leonid L. Fershtat
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. International Journal of Molecular Sciences is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. There is an Article Processing Charge (APC) for publication in this open access journal. For details about the APC please see here. Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

nitrogen heterocycles
azides
nitro compounds
mesoionic compounds
organic materials
cycloaddition and cycloreversion
oxidation
radical reactions
organic ligands
transition metal complexes

Published Papers (13 papers)

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Research

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19 pages, 4098 KiB

Open AccessArticle

Thermochemistry, Tautomerism, and Thermal Stability of 5,7-Dinitrobenzotriazoles

by Igor N. Melnikov, Vitaly G. Kiselev, Igor L. Dalinger, Alexey M. Starosotnikov, Nikita V. Muravyev and Alla N. Pivkina

Int. J. Mol. Sci. 2023, 24(6), 5330; https://doi.org/10.3390/ijms24065330 - 10 Mar 2023

Viewed by 1231

Abstract

Nitro derivatives of benzotriazoles are safe energetic materials with remarkable thermal stability. In the present study, we report on the kinetics and mechanism of thermal decomposition for 5,7-dinitrobenzotriazole (DBT) and 4-amino-5,7-dinitrobenzotriazole (ADBT). The pressure differential scanning calorimetry was employed to study the decomposition kinetics of DBT experimentally because the measurements under atmospheric pressure are disturbed by competing evaporation. The thermolysis of DBT in the melt is described by a kinetic scheme with two global reactions. The first stage is a strong autocatalytic process that includes the first-order reaction (E_a1^I = 173.9 ± 0.9 kJ mol⁻¹, log(A₁^I/s⁻¹) = 12.82 ± 0.09) and the catalytic reaction of the second order with E_a2^I = 136.5 ± 0.8 kJ mol⁻¹, log(A₂^I/s⁻¹) = 11.04 ± 0.07. The experimental study was complemented by predictive quantum chemical calculations (DLPNO-CCSD(T)). The calculations reveal that the 1H tautomer is the most energetically preferable form for both DBT and ADBT. Theory suggests the same decomposition mechanisms for DBT and ADBT, with the most favorable channels being nitro-nitrite isomerization and C–NO₂ bond cleavage. The former channel has lower activation barriers (267 and 276 kJ mol⁻¹ for DBT and ADBT, respectively) and dominates at lower temperatures. At the same time, due to the higher preexponential factor, the radical bond cleavage, with reaction enthalpies of 298 and 320 kJ mol⁻¹, dominates in the experimental temperature range for both DBT and ADBT. In line with the theoretical predictions of C–NO₂ bond energies, ADBT is more thermally stable than DBT. We also determined a reliable and mutually consistent set of thermochemical values for DBT and ADBT by combining the theoretically calculated (W1-F12 multilevel procedure) gas-phase enthalpies of formation and experimentally measured sublimation enthalpies. Full article

(This article belongs to the Special Issue Polynitrogen and Nitrogen-Oxygen Molecular Systems: Synthesis, Reactivity and Application)

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11 pages, 5173 KiB

Open AccessArticle

Unlocking Kuhn Verdazyls: New Synthetic Approach and Useful Mechanistic Insights

by Fedor E. Teslenko and Leonid L. Fershtat

Int. J. Mol. Sci. 2023, 24(3), 2693; https://doi.org/10.3390/ijms24032693 - 31 Jan 2023

Viewed by 1781

Abstract

An optimized synthetic protocol toward the assembly of Kuhn verdazyls based on an azo coupling of arenediazonium salts with readily available hydrazones followed by the base-mediated cyclization of in situ formed formazans with formalin was developed. The scope and limitations of the presented method were revealed. Some new mechanistic insights on the formation of Kuhn verdazyls were also conducted. It was found that in contradiction with previously assumed hypotheses, the synthesis of verdazyls was accomplished via an intermediate formation of verdazylium cations which were in situ reduced to leucoverdazyls. The latter underwent deprotonation under basic conditions to generate corresponding anions which coproportionate with verdazylium cations to furnish the formation of Kuhn verdazyls. The spectroscopic and electrochemical behavior of the synthesized verdazyls was also studied. Overall, our results may serve as a reliable basis for further investigation in the chemistry and applications of verdazyls. Full article

(This article belongs to the Special Issue Polynitrogen and Nitrogen-Oxygen Molecular Systems: Synthesis, Reactivity and Application)

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16 pages, 3204 KiB

Open AccessArticle

Straightforward and Efficient Protocol for the Synthesis of Pyrazolo [4,3-b]pyridines and Indazoles

by Vladislav V. Nikol’skiy, Mikhail E. Minyaev, Maxim A. Bastrakov and Alexey M. Starosotnikov

Int. J. Mol. Sci. 2023, 24(2), 1758; https://doi.org/10.3390/ijms24021758 - 16 Jan 2023

Viewed by 1294

Abstract

An efficient method for the synthesis of pyrazolo [4,3-b]pyridines has been developed on the basis of readily available 2-chloro-3-nitropyridines via a sequence of SNAr and modified Japp–Klingemann reactions. The method offers a number of advantages including utilization of stable arenediazonium tosylates, operational simplicity as well as combining the azo-coupling, deacylation and pyrazole ring annulation steps in a one-pot manner. An unusual rearrangement (C-N-migration of the acetyl group) was observed and a plausible mechanism was proposed based on the isolated intermediates and NMR experiments. In addition, the developed protocol was successfully applied to the synthesis of 1-arylindazoles combining the Japp–Klingemann reaction and cyclization of the resulting hydrazone as a one-pot procedure. Full article

(This article belongs to the Special Issue Polynitrogen and Nitrogen-Oxygen Molecular Systems: Synthesis, Reactivity and Application)

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11 pages, 29632 KiB

Open AccessArticle

N-Functionalization of 5-Aminotetrazoles: Balancing Energetic Performance and Molecular Stability by Introducing ADNP

by Jin Xiong, Jinjie Chang, Jinxiong Cai, Ping Yin and Siping Pang

Int. J. Mol. Sci. 2022, 23(24), 15841; https://doi.org/10.3390/ijms232415841 - 13 Dec 2022

Cited by 3 | Viewed by 1540

Abstract

5-aminotetrazole is one of the most marked high-nitrogen tetrazole compounds. However, the structural modification of 5-aminotetrazole with nitro groups often leads to dramatically decreased molecular stability, while the N-bridging functionalization does not efficiently improve the density and performance. In this paper, we report on a straightforward approach for improving the density of 5-aminotetrazole by introducing 4-amino-3,5-dinitropyrazole. The following experimental and calculated properties show that nitropyrazole functionalization competes well with energetic performance and mechanic sensitivity. All compounds were thoroughly characterized using IR and NMR spectroscopy, elemental analysis, and differential scanning calorimetry (DSC). Two energetic compounds (DMPT-1 and DMPT-2) were further confirmed by implementing single-crystal X-ray diffraction studies. Compound DMPT-1 featured a high crystal density of 1.806 g cm⁻³, excellent detonation velocity (v_D = 8610 m s⁻¹), detonation pressure (P = 30.2 GPa), and impact sensitivity of 30 J. Full article

(This article belongs to the Special Issue Polynitrogen and Nitrogen-Oxygen Molecular Systems: Synthesis, Reactivity and Application)

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11 pages, 1201 KiB

Open AccessArticle

Annulation of Perimidines with 5-Alkynylpyrimidines en Route to 7-Formyl-1,3-Diazopyrenes

by Stanislav V. Shcherbakov, Alexander V. Aksenov, Maksim V. Vendin, Viktoria Yu. Shcherbakova, Anna Yu. Ivanova, Maksim O. Shcheglov, Sergei N. Ovcharov and Michael Rubin

Int. J. Mol. Sci. 2022, 23(24), 15657; https://doi.org/10.3390/ijms232415657 - 10 Dec 2022

Viewed by 1063

Abstract

Unusual rearrangements were shown to accompany Brønsted acid-assisted peri-annulations of 1H-perimidines with 5-alkynylpyrimidines. These transformations take different routes depending on the nature of acetylene precursor, and lead to the formation of 7-formyl-1,3-diazopyrenes. Full article

(This article belongs to the Special Issue Polynitrogen and Nitrogen-Oxygen Molecular Systems: Synthesis, Reactivity and Application)

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21 pages, 4545 KiB

Open AccessArticle

Water-Soluble Salts Based on Benzofuroxan Derivatives—Synthesis and Biological Activity

by Elena Chugunova, Victoria Matveeva, Alena Tulesinova, Emil Iskanderov, Nurgali Akylbekov, Alexey Dobrynin, Ayrat Khamatgalimov, Nurbol Appazov, Lyazat Boltayeva, Bakhytzhan Duisembekov, Mukhtar Zhanakov, Yulia Aleksandrova, Tatyana Sashenkova, Elena Klimanova, Ugulzhan Allayarova, Anastasia Balakina, Denis Mishchenko, Alexander Burilov and Margarita Neganova

Int. J. Mol. Sci. 2022, 23(23), 14902; https://doi.org/10.3390/ijms232314902 - 28 Nov 2022

Cited by 2 | Viewed by 2230

Abstract

A series of novel water-soluble salts of benzofuroxans was achieved via aromatic nucleophilic substitution reaction of 4,6-dichloro-5-nitrobenzofuroxan with various amines. The salts obtained showed good effectiveness of the pre-sowing treatment of seeds of agricultural crops at concentrations of 20–40 mmol. In some cases, the seed treatment with salts leads not only to improved seed germination, but also to the suppression of microflora growth. Additionally, their anti-cancer activityin vitrohas been researched. The compounds with morpholine fragments or a fragment of N-dimethylpropylamine, demonstrated the highest cytotoxic activity, which is in good correlation with the ability to inhibit the glycolysis process in tumor cells. Two compounds 4e and 4g were selected for further experiments using laboratory animals. It was found that the lethal dose of 50% (LD₅₀) is 22.0 ± 1.33 mg/kg for 4e and 13.75 ± 1.73 mg/kg for 4g, i.e., compound 4e is two times less toxic than 4g, according to the mouse model in vivo. It was shown that the studied compounds exhibit antileukemia activity after a single intraperitoneal injection at doses from 1.25 to 5 mg/kg, as a result of which the average lifespan of animals with a P388 murine leukemia tumor increases from 20 to 28%. Thus, the water-soluble salts of benzofuroxans can be considered as promisingcandidates for further development, both as anti-cancer agents and as stimulants for seed germination and regulators of microflora crop growth. Full article

(This article belongs to the Special Issue Polynitrogen and Nitrogen-Oxygen Molecular Systems: Synthesis, Reactivity and Application)

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18 pages, 2906 KiB

Open AccessArticle

Acid-Switchable Synthesis of Trifluoromethylated Triazoles and Isoxazoles via Reaction of CF₃-Ynones with NaN₃: DFT Study of the Reaction Mechanism

by Vasiliy M. Muzalevskiy, Zoia A. Sizova, Mikhail S. Nechaev and Valentine G. Nenajdenko

Int. J. Mol. Sci. 2022, 23(23), 14522; https://doi.org/10.3390/ijms232314522 - 22 Nov 2022

Cited by 3 | Viewed by 1435

Abstract

A detailed study of the reaction of CF₃-ynones with NaN₃ was performed. It was found that the reaction permits the selective synthesis of either 4-trifluoroacetyltriazoles or 5-CF₃-isoxazoles. The chemoselectivity of the reaction was switchable via acid catalysis. The reaction of CF₃-ynones with NaN₃ in EtOH produced high yields of 4-trifluoroacetyltriazoles. In contrast, the formation of 5-CF₃-isoxazoles was observed under catalysis by acids. This acid-switchable procedure can be performed at sub-gram scale. The possible reaction mechanism was supported by DFT calculations. The synthetic utility of the prepared 4-trifluoroacetyltriazoles was demonstrated. Full article

(This article belongs to the Special Issue Polynitrogen and Nitrogen-Oxygen Molecular Systems: Synthesis, Reactivity and Application)

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8 pages, 2327 KiB

Open AccessArticle

Coordinative Combination of Nitroamine and Gem-Dinitromethyl with Fused Ring for Enhanced Oxygen Balances and Detonation Properties

by Xun Zhang, Yaxi Wang, Xinyuan Zhao, Chunlin He and Siping Pang

Int. J. Mol. Sci. 2022, 23(22), 14337; https://doi.org/10.3390/ijms232214337 - 18 Nov 2022

Viewed by 1287

Abstract

Oxygen balance and heat of formation are closely related to the nitrogen and oxygen content in a molecule and have a significant effect on the detonation performance of energetic materials. Here a new family of 1,2,4-triazolo [4,3-b][1,2,4,5]-tetrazine containing gem-dinitromethyl and nitroamine with high nitrogen-oxygen content was synthesized and characterized. Moreover, the structure of the guanidine salt (3) and TATOT salt (4) were confirmed by single-crystal X-ray diffraction. The nitrogen and oxygen content of ammonium salt 2 reached 82.5%, with a high density (1.805 g cm⁻³) and high detonation properties (D = 8900 m s⁻¹; P = 32.4 GPa), which were similar to those of RDX. Full article

(This article belongs to the Special Issue Polynitrogen and Nitrogen-Oxygen Molecular Systems: Synthesis, Reactivity and Application)

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13 pages, 5304 KiB

Open AccessArticle

Pyrolysis Kinetics and Combustion Behaviors of a High-Nitrogen Compound, 4,4′-Azobis(1,2,4-triazole)

by Qi Pan, Honglei Zhang, Xueyong Guo, Sen Sun and Shenghua Li

Int. J. Mol. Sci. 2022, 23(19), 11313; https://doi.org/10.3390/ijms231911313 - 25 Sep 2022

Cited by 4 | Viewed by 1308

Abstract

To study the thermal decomposition behavior of 4,4′-azobis(1,2,4-triazole) (ATRZ), the non-isothermal thermal decomposition kinetics of ATRZ were studied using the thermogravimetric–differential scanning calorimetry (TG–DSC) method. The TG–DSC of ATRZ was analyzed at heating rates of 5, 10, 15, and 20 K·min⁻¹ in an argon atmosphere. The thermal decomposition kinetic parameters at peak temperature (T_p), such as apparent activation energy (E_a) and pre-exponential factor (lgA) of ATRZ, were calculated using the Kissinger, Ozawa, and Satava–Sestak methods. E_a and lgA calculated using the Kissinger, Ozawa, and Satava–Sestak methods are very close, at 780.2 kJ·mol⁻¹/70.5 s⁻¹, 751.1 kJ·mol⁻¹/71.8 s⁻¹, and 762.1 kJ·mol⁻¹/71.8 s⁻¹, respectively. Using a combination of three methods, the reaction mechanism function g(α) of ATRZ was obtained. The results show that the decomposition temperature of ATRZ is about 310 °C, and the decomposition is rapidly exothermic. The pyrolysis path of ATRZ was investigated through a pyrolysis-gas chromatography mass spectrometry (PY-GC/MS) experiment. ATRZ has three different decomposition paths and finally generates N₂, HC-N-CH, N≡C-N, and HC=N-C≡N. The laser ignition combustion duration of ATRZ was 0.5033 s and the peak temperature was 1913 °C. The laser ignition combustion duration of ATRZ+CL-20 was 1.0277 s and the peak temperature was 2105 °C. The rapid energy release rate of ATRZ promotes the combustion energy release of CL-20. Full article

(This article belongs to the Special Issue Polynitrogen and Nitrogen-Oxygen Molecular Systems: Synthesis, Reactivity and Application)

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10 pages, 2098 KiB

Open AccessArticle

A Convenient Way to Quinoxaline Derivatives through the Reaction of 2-(3-Oxoindolin-2-yl)-2-phenylacetonitriles with Benzene-1,2-diamines

by Alexander V. Aksenov, Nikolai A. Arutiunov, Dmitrii A. Aksenov, Artem V. Samovolov, Igor A. Kurenkov, Nicolai A. Aksenov, Elena A. Aleksandrova, Daria S. Momotova and Michael Rubin

Int. J. Mol. Sci. 2022, 23(19), 11120; https://doi.org/10.3390/ijms231911120 - 22 Sep 2022

Cited by 3 | Viewed by 1456

Abstract

Microwave-assisted reaction between 2-(3-oxoindolin-2-yl)-2-phenylacetonitriles andbenzene-1,2-diamines leads to the high-yielding formation of the corresponding quinoxalines as sole, easily isolaable products. The featured transformation involves unusual extrusion of phenylacetonitrile molecule and could be performed in a short sequence starting from commonly available indoles and nitroolefins. [...] Read more.

(This article belongs to the Special Issue Polynitrogen and Nitrogen-Oxygen Molecular Systems: Synthesis, Reactivity and Application)

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19 pages, 6710 KiB

Open AccessArticle

Ultrasonic-Assisted Synthesis of Benzofuran Appended Oxadiazole Molecules as Tyrosinase Inhibitors: Mechanistic Approach through Enzyme Inhibition, Molecular Docking, Chemoinformatics, ADMET and Drug-Likeness Studies

by Ali Irfan, Ameer Fawad Zahoor, Shagufta Kamal, Mubashir Hassan and Andrzej Kloczkowski

Int. J. Mol. Sci. 2022, 23(18), 10979; https://doi.org/10.3390/ijms231810979 - 19 Sep 2022

Cited by 11 | Viewed by 2430

Abstract

Furan-oxadiazole structural hybrids belong to the most promising and biologically active classes of oxygen and nitrogen containing five member heterocycles which have expanded therapeutic scope and potential in the fields of pharmacology, medicinal chemistry and pharmaceutics. A novel series 5a–j of benzofuran-oxadiazole molecules incorporating S-alkylated amide linkage have been synthesized using ultrasonic irradiation and screened for bacterial tyrosinase inhibition activity. Most of the synthesized furan-oxadiazole structural motifs exhibited significant tyrosinase inhibition activity in the micromolar range, with one of the derivatives being more potent than the standard drug ascorbic acid. Among the tested compounds, the scaffold 5a displayed more tyrosinase inhibition efficacy IC₅₀ (11 ± 0.25 μM) than the ascorbic acid IC₅₀ (11.5 ± 0.1 μM). Compounds 5b, 5c and 5d efficiently inhibited bacterial tyrosinase with IC₅₀ values in the range of 12.4 ± 0.0–15.5 ± 0.0 μM. The 2-fluorophenylacetamide containing furan-oxadiazole compound 5a may be considered as a potential lead for tyrosinase inhibition with lesser side effects as a skin whitening and malignant melanoma anticancer agent. Full article

(This article belongs to the Special Issue Polynitrogen and Nitrogen-Oxygen Molecular Systems: Synthesis, Reactivity and Application)

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7 pages, 1599 KiB

Open AccessArticle

Boosting the Energetic Performance of Trinitromethyl-1,2,4-oxadiazole Moiety by Increasing Nitrogen-Oxygen in the Bridge

by Peng Chen, Hui Dou, Chunlin He and Siping Pang

Int. J. Mol. Sci. 2022, 23(17), 10002; https://doi.org/10.3390/ijms231710002 - 2 Sep 2022

Cited by 5 | Viewed by 1772

Abstract

The trinitromethyl moiety is a useful group for the design and development of novel energetic compounds with high nitrogen and oxygen content. In this work, by using an improved nitration method, the dinitromethyl precursor was successfully nitrated to the trinitromethyl product (2), and its structure was thoroughly characterized by FTIR, NMR, elemental analysis, differential scanning calorimetry, and single-crystal X-ray diffraction. Compound 2 has a high density (1.897 g cm⁻³), high heat of formation (984.8 kJ mmol⁻¹), and a high detonation performance (D: 9351 m s⁻¹, P: 37.46 GPa) that may find useful applications in the field of high energy density materials. Full article

(This article belongs to the Special Issue Polynitrogen and Nitrogen-Oxygen Molecular Systems: Synthesis, Reactivity and Application)

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Review

Jump to: Research

22 pages, 17704 KiB

Open AccessReview

Recent Advances in the Chemistry of Saturated Annulated Nitrogen-Containing Polycyclic Compounds

by Victor Yu. Kirsanov and Elena B. Rakhimova

Int. J. Mol. Sci. 2022, 23(24), 15484; https://doi.org/10.3390/ijms232415484 - 7 Dec 2022

Cited by 3 | Viewed by 1686

Abstract

This review is devoted to the analysis of works published over the past 20 years on the chemistry of saturated annulated nitrogen-containing polycyclic compounds, the molecules of which consist of four, five, six, and seven cycles, and contain from one to eight endocyclic [...] Read more.

(This article belongs to the Special Issue Polynitrogen and Nitrogen-Oxygen Molecular Systems: Synthesis, Reactivity and Application)

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