Ананьев Иван Вячеславович
Базовая кафедра элементоорганической химии Института элементоорганических соединений им. А.Н. Несмеянова РАН
Профессиональные интересы
Должности
- Профессор — Базовая кафедра элементоорганической химии Института элементоорганических соединений им. А.Н. Несмеянова РАН
Био
- · Начал работать в НИУ ВШЭ в 2019 году.
- · Научно-педагогический стаж: 14 лет.
Образование
- 2024 · Доктор физико-математических наук
- 2013 · Кандидат наук
- 2010 · Специалитет: Российский химико-технологический университет им. Д.И. Менделеева, специальность «Химия», квалификация «Химик»
Опыт работы
- · 2022 - н.в.: Институт общей и неорганической химии РАН им. Н.С. Курнакова:
- · ведущий научный сотрудник, заведующий лабораторией
- · 2010 - н.в.: Институт элементоорганических соединений им. А.Н. Несмеянова:
- · старший научный сотрудник
Награды и поощрения
- · Надбавка за публикацию в журнале из Списка А (и приравненном к нему научном издании) (2025–2026, 2024–2025, 2023–2024)
- · Надбавка за публикацию в международном рецензируемом научном издании (2022–2023, 2021–2022, 2019–2021)
- · Лучший преподаватель — 2020–2023
Гранты и проекты
- — · на соискание учёной степени кандидата наук
Идентификаторы исследователя
- ORCID:
0000-0001-6867-7534 - ResearcherID:
M-1918-2015 - SPIN РИНЦ:
3476-2887 - Google Scholar: https://scholar.google.com/citations?user=Ey7Zm-EAAAAJ&hl=ru
- Scopus AuthorID:
6508039780
Публикации (51)
Novel family of nitrogen-rich energetic (1,2,4-triazolyl) furoxan salts with balanced performance
2022 · ARTICLE · en
Nitrogen-rich energetic materials comprised of a combination of several heterocyclic subunits retain their leading position in the field of materials science. In this regard, a preparation of novel high-energy materials with balanced set of physicochemical properties is highly desired. Herein, we report the synthesis of a new series of energetic salts incorporating a (1,2,4-triazolyl) furoxan core and complete evaluation of their energetic properties. All target energetic materials were well characterized with IR and multinuclear NMR spectroscopy and elemental analysis, while compound 6 was further characterized by single-crystal X-ray diffraction study. Prepared nitrogen-rich salts have high thermal stability (up to 232°C), good experimental densities (up to 1.80 g cm−3) and high positive enthalpies of formation (344–1,095 kJ mol−1). As a result, synthesized energetic salts have good detonation performance (D = 7.0–8.4 km s−1; p = 22–32 GPa), while their sensitivities to impact and friction are quite low.
Renaissance of dinitroazetidine: novel hybrid energetic boosters and oxidizers
2022 · ARTICLE · en
Nitrogen-oxygen organic materials constitute an important family of multipurpose high-energy materials. However, the preparation of energetic boosters and oxidizers for various civil and space technologies remains a challenging task and such materials usually require special precautions and fine tunability of their functional properties. To find a balance between energy and safety while retaining the oxidizing ability of target energetic materials, novel hybrid organic compounds comprising furoxan and 3,3-dinitroazetidine scaffolds enriched with additional nitro groups were synthesized. The prepared 3-(3,3-dinitroazetidinoyl)-4-nitrofuroxan and 3,3-dinitro-1-(2,2,2-trinitroethyl)azetidine have high nitrogen-oxygen contents (75-79%), positive oxygen balance to CO (up to +10.3%) and good experimental densities (1.75-1.80 g cm−3). A combination of superior detonation performance (D = 8.3-8.5 km s−1 and P = 32-33 GPa) and moderate mechanical sensitivity enables the application potential of these energetic materials as booster explosives or oxidizers. Additionally, their functional properties remain essentially competitive with other oxygen-rich energetic materials (pentaerythritol tetranitrate, ammonium dinitramide, and tetranitratoethane). Hirshfeld surface calculations supported by energy framework plots were also performed to better understand the relationship between the molecular structure and stability/sensitivity. This work unveils novel directions in the construction of balanced energetic boosters and oxidizers for various applications. © 2022 The Royal Society of Chemistry.
Simple and energetic: Novel combination of furoxan and 1,2,4-triazole rings in the synthesis of energetic materials
2022 · ARTICLE · en
Two novel representatives of energetic (1,2,4-triazolyl)furoxans were prepared from the readily available (furoxanyl)amidrazones. Synthesized compounds were thoroughly characterized with IR and multinuclear NMR spectroscopy, elemental analysis and X-ray diffraction data. Analysis of structural features supported by quantum-chemical calculations revealed the main reasons for experimentally observed difference in thermal stability and mechanical sensitivity of both compounds. It was found that 3-cyano-4-(1H-1,2,4-triazol-3-yl)furoxan is more thermally stable (Td: 229 °C) than 4-azido-3-(1H-1,2,4-triazol-3-yl)furoxan (Td: 154 °C) and the latter compound is also more sensitive to impact and friction. In addition, both heterocyclic assemblies have high detonation parameters (vD: 7.0–8.0 km·s−1; p: 22–29 GPa) exceeding those of benchmark explosives trinitrotoluene and hexanitrostilbene which enable their usability for various energetic applications.
Rational Screening of Cocrystals using Thermal Analysis: Benchmarking on Energetic Materials
2022 · ARTICLE · en
Cocrystal design is an important and well-developed approach in the pharmaceutical industry. Energetic materials can be thought of as unique and challenging objects for cocrystal engineering since abundant explosophoric functionalities prevent exploiting common supramolecular synthons. Screening of cocrystal formation using thermal analysis methods is investigated. A few approaches from the literature are combined in a single procedure that allows for automation, high-throughput screening, and the usage of milligrams of material. To estimate the accuracy of the screening procedure, we compiled available literature data on 213 cocrystals with energetic or very similar to energetic materials. The recommended procedure can detect cocrystal formation in 75% cases (with no false positives), according to a smaller sample data set of 28 cocrystal-forming systems. The procedure was then used to screen for novel cocrystals among several acidic energetic materials, ammonium and hydroxylammonium energetic salts, 3-nitro-1,2,4-triazole as a coformers, and 13 cocrystals were discovered. Then, using the traditional solution procedure, eight novel cocrystals were prepared, and their X-ray structures were reported. One of the cocrystals discovered, a complex of promising energetic material, dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (also known as TKX-50) with 18-crown-6, is the first cocrystal of TKX-50 with a reported X-ray structure so far. Overall, we present a unified procedure of thermal screening for cocrystals and salts; benchmarking on challenging objects for cocrystal design (energetic materials) shows its high performance.
Long-range supramolecular synthon polymorphism: a case study of two new polymorphic cocrystals of Ph2Te2–1,4-C6F4I2
2022 · ARTICLE · en
Along with the reported earlier cocrystal of diphenyl ditelluride (Ph2Te2) and halogen bond donor 1,4-diiodo-tetrafluorobenzene (p-DITFB) 1α, its two new polymorphic forms (1β and 1γ) present a rare case of long-range supramolecular synthon module polymorphism. In contrast to I⋯Te halogen bonding (HaB) in the earlier reported form 1α, their main building motif is I⋯π(Ph) HaB. The lattice energy calculations for this polymorphic triad suggest the 1α–1β–1γ sequence from the kinetic to thermodynamic form. Cocrystal 1β appeared completely isostructural with the Ph2Se2·(p-DITFB) cocrystal and the double chains of Ph2Te2 molecules in 1β reproduce the packing of the pure Ph2Se2 and the pattern of Ph2Se2 chains in Ph2Se2·p-DITFB. Single chains of Ph2Te2 in the 1γ form feature only partial similarity with 1β but together, these three polymorphic cocrystals along with the native Ph2Te2 and Ph2Se2 compose a rather detailed and remarkable structural landscape. It suggests the putative polymorphic forms of Ph2Te2 and Ph2Se2, which were studied in silico by periodic DFT. The energy framework approach appeared to be a useful and illustrative way to analyze the correlation between the energetic structure of co-crystals 1β and 1γ and their noticeably different habits.
Hybrid iodobismuthates code: adapting the geometry of Bi polyhedra to weak interactions
2021 · ARTICLE · en
The crystal structure of the new iodobismuthate (PyPy)2(PyPyH)2Bi6I26 was found to consist of unusual hexanuclear [Bi6I26]6– anions containing the linear I4 2– unit, and the experimental Bi–I bond lengths in this anion were used to obtain the relationship between bond length and bond energy. A statistical analysis of 229 crystal structures of iodobismuthates, based on the quantum chemically estimated strength of Bi–I bonds, revealed that the total energy of the Bi3+ polyhedron remains virtually constant at 64 ± 2 kcal mol–1, regardless of its geometry within this family of materials. Thus, the polyhedron geometry flexibly adapts to the relatively weak interactions between iodobismuthate anions and embedded cations.
Design and Synthesis of Nitrogen-Rich Azo-Bridged Furoxanylazoles as High-Performance Energetic Materialsv
2021 · ARTICLE · en
cA series of novel energetic materials comprising of azo-bridged furoxanylazoles enriched with energetic functionalities was designed and synthesized. These high-energy materials were thoroughly characterized by IR and multinuclear NMR (1H, 13C, 14N) spectroscopy, high-resolution mass spectrometry, elemental analysis, and differential scanning calorimetry (DSC). The molecular structures of representative amino and azo oxadiazole assemblies were additionally confirmed by single-crystal X-ray diffraction and X-ray powder diffraction. A comparison of contributions of explosophoric moieties into the density of energetic materials revealed that furoxan and 1,2,4-oxadiazole rings are the densest motifs while the substitution of the azide and amino fragments on the nitro and azo ones leads to an increase of the density. Azo bridged energetic materials have high nitrogen-oxygen contents (68.8–76.9 %) and high thermal stability. The synthesized compounds exhibit good experimental densities (1.62–1.88 g cm−3), very high enthalpies of formation (846–1720 kJ mol−1), and, as a result, excellent detonation performance (detonation velocities 7.66–9.09 km s−1 and detonation pressures 25.0–37.7 GPa). From the application perspective, the detonation parameters of azo oxadiazole assemblies exceed those of the benchmark explosive RDX, while a combination of high detonation performance and acceptable friction sensitivity of azo(1,2,4-triazolylfuroxan) make it a promising potential alternative to PETN.
Design and Synthesis of Nitrogen‐Rich Azo‐Bridged Furoxanylazoles as High‐Performance Energetic Materials
2021 · ARTICLE · en
A series of novel energetic materials comprising of azo-bridged furoxanylazoles enriched with energetic functionalities was designed and synthesized. These high-energy materials were thoroughly characterized by IR and multinuclear NMR (1H, 13C, 14N) spectroscopy, high-resolution mass spectrometry, elemental analysis, and differential scanning calorimetry (DSC). The molecular structures of representative amino and azo oxadiazole assemblies were additionally confirmed by single-crystal X-ray diffraction and X-ray powder diffraction. A comparison of contributions of explosophoric moieties into the density of energetic materials revealed that furoxan and 1,2,4-oxadiazole rings are the densest motifs while the substitution of the azide and amino fragments on the nitro and azo ones leads to an increase of the density. Azo bridged energetic materials have high nitrogen-oxygen contents (68.8–76.9 %) and high thermal stability. The synthesized compounds exhibit good experimental densities (1.62–1.88 g cm−3), very high enthalpies of formation (846–1720 kJ mol−1), and, as a result, excellent detonation performance (detonation velocities 7.66–9.09 km s−1 and detonation pressures 25.0–37.7 GPa). From the application perspective, the detonation parameters of azo oxadiazole assemblies exceed those of the benchmark explosive RDX, while a combination of high detonation performance and acceptable friction sensitivity of azo(1,2,4-triazolylfuroxan) make it a promising potential alternative to PETN.
Revisiting van der Waals Radii: From Comprehensive Structural Analysis to Knowledge‐Based Classification of Interatomic Contacts
2020 · ARTICLE · en
Weak noncovalent interactions are responsible for structure and properties of almost all supramolecular systems, such as nucleic acids, enzymes, and pharmaceutical crystals. However, the analysis of their significance and structural role is not straightforward and commonly requires model studies. Herein, we describe an efficient and universal approach for the analysis of noncovalent interactions and determination of van der Waals radii using the line-of-sight (LoS) concept. The LoS allows to unambiguously identify and classify the "direct" interatomic contacts in complex molecular systems. This approach not only provides an improved theoretical base to molecular "sizes" but also enables the quantitative analysis of specificity, anisotropy, and steric effects of intermolecular interactions.
Route to 1,2,4-and 1,2,5-oxadiazole ring assemblies via a one-pot condensation/oxidation protocol
2020 · ARTICLE · en
A novel one-pot approach for the synthesis of 1,2,4- and 1,2,5-oxadiazole ring assemblies has been developed. The synthetic strategy involves the condensation of furoxanyl amidoximes with aldehydes and subsequent iodine-mediated oxidation of the intermediate 1,2,4-oxadiazolines. The analogous reaction of 4-aminofuroxanyl-3-carboxamidoxime results not only in formation of the 1,2,4-oxadiazole subunit, but also rearrangement of the furoxan ring to the furazan one, which is the first example of a Lewis acid-promoted rearrangement in a furoxan series
Курсы (3)
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Теоретическая неорганическая химия и химия элементов · 2 раза
2023/2024, 2022/2023 · Бакалавриат · рус
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Квантовая химия
2022/2023 · Бакалавриат · рус
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Теоретическая неорганическая химия
2021/2022 · Бакалавриат · рус