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Project titleIodonium salts: preparation, structure, and application for the design of new functional materials for organic electronics, photonic and plasmonic.

Research area 03 - CHEMISTRY AND MATERIAL SCIENCES, 03-101 - Synthesis, structure and reactivity of organic compounds

Keywordsiodonium salts, fused heterocycles, covalent surface modification, surface properties, smart materials, flow synthesis

Annotation
The main goal of the project is the systematic investigation of fundamental aspects of synthesis and application of iodonium salts in the design of new smart materials. Utilization of organic components in this field is often limited by the high price of products of fine organic synthesis. Traditionally, iodonium salts acquisition has always been associated with expensive oxidizing agents and solvents (e.g. m-chloroperbenzoic acid, trifluoroethanol etc.), significantly restricting incorporation of such reagents in the future. That is why one of the key objectives of the project is the development of easy, effective and cheap methods of iodonium salts synthesis with the incorporation of flow chemistry along with cheap and cost-effective oxidants. During the research, intelligent algorithms of optimization are to be used in order to minimize the cost of iodonium salts acquisition. Moreover, during the course of the project not only new methods of iodonium salts acquisition will be proposed, but also new methodologies for their transformation into useful products will be formulated (valuable fluoro-derivatives, in particular). Proposed approaches to synthesis of iodonium salts will also allow to acquire a wide variety of their cyclic derivatives containing heteroaromatic fragments. Acquired cyclic iodonium salts will be used in reactions of synthesis of fused heterocyclic thiophenes and pyrroles, as well as carbocyclic systems. Such compounds show a lot of promise as materials for organic electronics. The methods are of special interest for modification of tetra[3,4]thienylene, because they will allow to create new methods of acquisition of cyclic oligothiophenes, along with corresponding selenium and pyrrole derivatives. The structure of these substances, as well as the structure of cyclic iodonium salts, will be characterized using modern methods, including quantum-chemical analysis. Acquired methodologies for iodonium salts synthesis will form the basis for design of new generation of materials with desired properties. Due to high demand for materials with predesigned properties, methods of surface modification using highly reactive organic compounds become more and more promising. In the course of this project it is planned to develop a number of methods for covalent modification of thin metal films and polymer materials to create surfaces with desired properties. Special attention will be paid to the combination of nanostructured surfaces acquisition with their further covalent modification to acquire femtostructured surfaces. New methods for modification using surface plasmon catalysis , photochemistry and classical principals of iodonium salts activation will be proposed during the course of the project. As a whole, this research is a full-cycle interdisciplinary endeavor devoted to both fundamental aspects of iodonium salts chemistry and its applications. The project will be carried out in cooperation with Moscow State University, University of Cardiff, Institute of Chemical Research of Catalonia, Tarragona and University of Chemistry and Technology, Prague.

Expected results
In the course of the project, it is planned to acquire new results of high practical and fundamental importance, such as: 1. New simple and effective methods for iodonium salts synthesis using mild and ecofriendly oxidizing agents. Such methods are practically relevant for further utilization of iodonium salts in new materials synthesis, as well possess high fundamental significance as the first protocol of iodonium salts generation via flow synthesis. 2. Development and synthesis of new kinds of cyclic iodonium salts containing heterocyclic fragments, and their complex structural and chemical analysis with incorporation of both theoretical and empirical approaches. Relations between structure and chemical properties of acquired salts will have apparent fundamental value both for iodonium compounds chemistry and development of new methodologies for the synthesis of fused heterocyclic systems. 3. Methods for generation of complex fused heterocyclic systems as a result of reactions of cyclic iodonium salts with various heteroatom sources (S, Se, amine derivatives etc.), leading to the formation of new circulenes, among other products. Structure and electron composition of acquired molecules will be analyzed using experimental and theoretical methods. 4. New methods and approaches to covalent modification of thin metal film surfaces with iodonium salts of different structure. Also, it is planned to investigate the mechanism of covalent modification selectivity, the influence of various substituting groups on organic layer structure and composition. Also, a comparative analysis of the structure of organic layers received using iodonium and diazonium salts will be carried out. 5. Synthesis of a new generation of smart materials with the surface modified with acquired iodonium salts and structured on micro-, nano- and femto-levels. Methodologies for design of materials with controlled and changeable wettability and icephobicity for sensoric, biocatalytic and construction technologies will be developed.

Annotation of the results obtained in 2019
The third year of project implementation has been dedicated to the continuation and finalization of previously started projects. Thus, we successfully continued the study of flow-based procedures for the preparation and synthetic application of bis-(trifluoroacetoxy)iodobenzenes. For instance, we demonstrated the possibility of carrying out the arylation of ketones in the flow reactor. Moreover, we continued our research dedicated to the synthetic application of hypervalent iodine compounds containing short contact between I and N. The high reactivity of these compounds forced us to investigate the thermal stability of N-I reagents in comparison with traditional O-coordinated compounds. We found that the reagents containing N-ligand exhibited enhanced stability and the absence of explosive effects under thermal decomposition, which makes it the perfect candidate for further applications in organic synthesis. During the third year of project implementation, we also explored the preparation of cyclic phenylimidazole iodonium salts and found the conditions for the isolation of water-soluble hydrosulfates. As we demonstrated, the prepared iodonium salts are able to react with sulfur with the formation of merit polyannelated heterocyclic systems. The general applicability of the synthetic method has also been demonstrated. A considerable part of the research has been dedicated to the in-depth evaluation of the mechanism explaining the observing effects in the plasmon-assisted decomposition of iodonium salts. We carefully studied the mechanism of the process, using experimental and theoretical techniques. We found that the plasmon energy is able to change the reaction pathways and led to the highly regioselective decomposition of iodonium salts. The observed effects open a new bright opportunity for the utilization of plasmon energy in the organic synthesis. Despite the mechanistic study, we sufficiently improved the method for the spatially-selective surface modification of anisotropic nanoparticles and applied the prepared material for the detection of amphiphilic molecules. Last but not least, our findings in the field of superhydrophobic materials allow us to create a novel porous sponge with an extremely high water contact angle using magnetic nanoparticles and surface modification. The prepared sponges demonstrated enhanced properties towards selective sorption of organic solvents and oils from water (including stabilized and non-stabilized emulsions).

Publications

1. A. Boelke, Y.A. Vlasenko, M.S. Yusubov, B.J. Nachtsheim, P.S. Postnikov Thermal stability of N-heterocycle-stabilized iodanes – a systematic investigation Beilstein Journal of Organic Chemistry, 2019, 15, 2311–2318 (year - 2019) https://doi.org/10.3762/bjoc.15.223

2. AO.Guselnikova, E.Miliutina, R.Elashnikov, V.Burtsev, M.M.Chehimi, V.Svorcik, M.Yusubov, O.Lyutakov, P.Postnikov Chemical modification of gold surface via UV-generated aryl radicals derived 3,5-bis(trifluoromethyl)phenyl)iodonium salt Progress in Organic Coatings, Volume 136, November 2019, 105211 (year - 2019) https://doi.org/10.1016/j.porgcoat.2019.105211

3. O. Guselnikova, A. Barras, A.Addad, E. Sviridova, S. Szunerits, P. Postnikov, R. Boukherroub Magnetic polyurethane sponge for efficient oil adsorption and separation of oil from oil-in-water emulsions Separation and Purification Technology, Volume 240, 1 June 2020, 116627 (year - 2020) https://doi.org/10.1016/j.seppur.2020.116627

4. - Ученые ТПУ разработали супергидрофобную губку для сбора нефти РИА Томск, - (year - )

5. - У нас нет посредственностей Научная Россия, "В мире науки" №12, 2019 (year - )

6. - Ученые ТПУ изобрели водоотталкивающую губку для ликвидации разливов нефти Интерфакс, - (year - )

7. - Superhydrophobic magnetic sponge to help purify water from oil products ChemEurope, - (year - )

8. - Цитируемые ученые: лесные пожары, керамика для добычи нефти и противоопухолевые агенты ТПУ, https://news.tpu.ru/news/2019/11/27/35542/ (year - )

Annotation of the results obtained in 2017
During the first year of project implementation, we developed a range of new methods and materials in the field of organic chemistry and materials sciences. We proposed synthetic approaches to the polyvalent iodine compounds as well as the novel reagents based on heterocyclic compounds, which allows to sufficiently expanding the organic chemistry toolbox. Moreover, the synthetic applicability of proposed reagents have been demonstrated in the reactions of heterocyclization with the formation of merit annealed heterocycles. The important part of project was dedicated to careful evaluation of the interaction between cyclic iodonium salts and nucleophiles using experimental and theoretical approaches, which allows revising the modern aspects of substitution mechanisms and explain the observed selectivity. During project implementation, we developed a novel methods of surface functionalization by iodonium salts under plasmon-catalysis. We prepared a new functional materials based on optic fibers with antibiofouling properties, which can be potentially applied in the media with high concentrations of biomolecules. Moreover, we evaluated the influence of surface organic groups on the distribution of nanoparticles of the modified surface. Based on these findings, we proposed a new method for the creation of periodic structures with large area. On the first year of project we suggested a new approaches for the preparation of composite “smart” materials with surface changeable surface properties driven by electric field (wettability, adhesion of water and organic solvents, self-cleaning).

Publications

1. Burtsev V., Marchuk V., Kugaevskiy A., Guselnikova O., Elashnikov R., Miliutina E., Postnikov P., Svorci V., Lyutakov O. Hydrophilic/hydrophobic surface modification impact on colloid lithography: Schottky-like defects, dislocation, and ideal distribution Applied Surface Science, 433, 443–448 (year - 2018) https://doi.org/10.1016/j.apsusc.2017.10.055

2. Guselnikova O.A., Elashnikov R.; Postnikov P.S.; Svorcik V., Lyutakov O. Smart, piezo-responsive PVDF/PMMA surface with triggerable water/oil wettability and adhesion ACS Applied Materials & Interfaces, - (year - 2018)

3. Miliutina E., Guselnikova O., Bainova P., Kalachyova E., Elashnikov R., Yusubov M.S., Zhdankin V.V., Postnikov P., Švorčík V., Lyutakov O. Plasmon‐Assisted Activation and Grafting by Iodonium Salt: Functionalization of Optical Fiber Surface Advanced Materials Interfaces, 1800725 (year - 2018) https://doi.org/10.1002/admi.201800725

4. Yusubov M.S., Soldatova N.S., Postnikov P.S., Valiev R.R., Svitich D.Yu., Yusubova R.Y., Yoshimura A., Wirth T., Zhdankin V.V. Reactions of 1‐Arylbenziodoxolones with Azide Anion: Experimental and Computational Study of Substituent Effects European Journal of Organic Chemistry, Volume 2018, Issue 5, Pages 640-647 (year - 2018) https://doi.org/10.1002/ejoc.201701595

5. - Ювелирная химия для органической электроники За Кадры, 16 октября 2017 №12 (3462) (year - )

Annotation of the results obtained in 2018
The second year of the project implementation was devoted to the additional investigations (started in the first year) and the development of new methods and approaches to the application of the iodonium salts chemistry in organic chemistry and the design of new functional materials. Previously developed method for the iodonium salts synthesis was applied for the preparation of a wide range of iodonium salts, including cyclic salts using advanced optimization methods. In addition, we extended works focused on reactivity research of new polyvalent iodine reagents containing an N-I bond, and their structural features (the existence of rotamers and their rapid interconversion at room temperature) were studied. We also carried out fundamental research focused on the interaction of plasmon with organic compounds – in the framework of research, it was shown that plasmon resonance is able to induce decomposition of iodonium salts on the surface and influence the selectivity of the homolysis reaction. Impressing obtained result allows us to re-evaluate the value of plasmon-induced reactions. In practical terms, the obtained result allows us to consider as modification reagents more economically available asymmetric iodonium salts for the modification of plasmon-active surfaces. To study the limits of applicability of iodonium salts in surface modification reactions, we proposed a new method of covalent modification of the noble metals surface by iodonium salts using UV irradiation. This method is simple and can be used for selective surface patterning with organic functional groups. Finally, differences in the reactivity of the iodonium and diazonium salts enable us to develop a spatial-selective procedure for the modification of the anisotropic plasmon-active surface (such as gold nanorods), that will result in the design of new-concept approaches to control the surface properties of nanomaterials.

Publications

1. N.S. Soldatova, P.S. Postnikov, M.S. Yusubov, T. Wirth Flow Synthesis of Iodonium Trifluoroacetates through Direct Oxidation of Iodoarenes by Oxone® European Journal of Organic Chemistry, Volume 2019, Issue 10, Pages 2081-2088 (year - 2019) https://doi.org/10.1002/ejoc.201900220

2. Yu.A. Vlasenko, P.S. Postnikov, M.E. Trusova, A. Shafir, V.V. Zhdankin, A. Yoshimura, M.S. Yusubov Synthesis of Five-Membered Iodine–Nitrogen Heterocycles from Benzimidazole-Based Iodonium Salts Journal of Organic Chemistry, 19, 83, 12056-12070 (year - 2018) https://doi.org/10.1021/acs.joc.8b01995

3. - Ученые ТПУ защитили оптоволокно от "налипающих" на него биомолекул РИА Томск, - (year - )

4. - Исследователи ТПУ вместе с коллегами из Чехии научились быстро управлять смачиваемостью материалов Научная Россия, - (year - )

5. - Как защитить оптические волокна от биомолекул Стимул, - (year - )

6. - ТО МОКНЕТ, ТО СОХНЕТ Поиск, - (year - )

7. - Ученые ТПУ создали "умный" материал с контролируемой смачиваемостью ИнноТомск, - (year - )