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COMMON PART

Project Number20-73-20015

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

Project LeadPostnikov Pavel

AffiliationNational Research Tomsk Polytechnic University,

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

PROJECT CONTENT

Annotation
The project is dedicated to the development of ideas and new concepts for the application of reagents based on hypervalent iodine in organic chemistry and the design of new materials during the first 3 years of the project. Thus, the project is an interdisciplinary study dedicated to both fundamental aspects of the synthesis of new hypervalent iodine reagents, and their application in organic chemistry and the design of new smart materials. One of the most important trends in modern chemistry and materials technology is the design of materials with controlled and tunable surface properties. The development of these technologies demands the attention of researchers to the fine tuning of surface properties, which could not be achieved with traditional reagents. During the first stages of the project, we propose an alternative to traditional reagents - iodonium salts, which are reactive for the surface covalent modification under the external stimuli (especially light and plasmon). Further, we plan to develop modification methods using these reagents and utilize them to new materials, including MXs and other 2D materials (for example, graphene). As part of this project, we plan to synthesize new hydrophobic and amphiphilic nanomaterials using a combination of different reagents. In addition, we plan to further improve synthesis methods of new hypervalent iodine reagents for further application in organic chemistry and materials science. At the same time, our results on plasmon activation of iodonium salts will allow us to develop conceptually new approaches to their synthetic application. The high regioselectivity of C-I bond homolysis under plasmon will lead to the development of a number of new synthetic methods using plasmon-active nanomaterials as a catalyst. As part of this project, we plan to develop new catalytic systems based on a combination of hypervalent iodine compounds with light-sensitive structures (nanoscale or metal-organic). This tendency of chemistry and materials science has a high scientific novelty and significance for industrial applications. The transferring of organic synthesis methodology into the design of new materials will make significant progress in the development of breakthrough technologies, and the reverse transferring - to develop conceptually new methods of transformation (including highly selective) of organic molecules. The project is based entirely on previous results and presents a continuation of the already accomplished project.

Expected results
During the project realization we are going to get the following results: 1. A novel approach to surface modification of 2D materials with iodonium and diazonium salts and to evaluate properties and applicability of new materials. Nowadays, the 2D materials attract interest due to their special properties and the wide scope of application. Moreover, 2D materials are of particular interest in technology for the design of high capacity condensers and batteries. We plan to develop novel methods of covalent modification of graphene (and graphene-like materials) and MXenes as materials for electronics and energy-efficient technology. Significantly, that fine tuning of functional groups on MXenes surface simplifies the design of the useful devices. Thus, proposal results are important for basic and engineering science due to the development of approaches to covalent modification of 2D materials and its application in innovative economics. 2. Plasmon-induced reactions of iodoarenes and hypervalent iodine compounds for organic chemistry and design of novel materials. We plan to develop approaches to plasmon-induced reactions of organic substrates based on our results in the mechanistic study of plasmon-catalyzed organic reaction. We are going to solve two main issues: 1. Use of plasmon-induced homolysis of iodonium salts in the design of new materials (including the application of the effects of local plasmonic "hot spots" for selective modifications); 2. Usage of plasmon-active nanomaterials for catalysis of organic reactions via the formation of aryl-radicals. We suppose that plasmon-active materials are alternative to traditional photocatalysts due to the simplicity of synthesis and usage of nanoparticles in comparison to photoactive complexes. 3. New reagents based on hypervalent organoiodine ligands for catalytic reactions of organic compounds. Further study in this project will be aimed at the development of a new photo- and electrochemical reactions. Our previous results in the synthesis of N-coordinated iodanes allow designing of new complex containing either hypervalent iodine or ligand moieties for complexation with transition metal (for instance, ruthenium). It allows getting new basic knowledge about the reactivity of hybrid catalysts based on hypervalent iodine compounds. These results are important for organic chemistry and hypervalent iodine chemistry. Nowadays there are plenty photocatalyzed reactions with hypervalent iodine reagents and photoactive complexes of transition metals. Drawbacks of these reactions for wide applications involve the usage of the excess of hypervalent iodine reagents. In our opinion, hybrid catalytic systems can be applied in photoredox and electrochemical reactions. The result of this work allows to wider applicability of hypervalent iodine compound in catalysis. Thus, the importance of expected results accords to current trends in chemistry and material science. Interdisciplinary research and already obtained results allow to get proposed results in a short time and report it in world-leading scientific journals.

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