Laboratory 2-3 "Synthesis and reactivity of metalloporphyrins in solutions"

Scientific direction: 
Synthesis, chemical structure and reactivity of aromatic macrocyclic compounds in solutions
Phone: 
+7 (4932) 336990

 

Main research topics:
  • Synthesis of new molecular receptors of small molecules and catalytic systems on the basis of mixed porphyrin-containing complex compounds
  • Structure, chemical reaction mechanisms, reactivity of higher substituted porphyrins and functional materials synthesis on their basis 
  • Porphyrinates of precious metals. Synthesis and investigation of coordinative and applied properties 
  • Complexes of manganese with substituted porphin, porphirazin and phthalocyanine as perspective models of natural catalases
  • Chemical stability and catalytic properties of manganese-porphyrins with various types of substitution in aromatic macrocycle

 

Subject  “Synthesis of new molecular receptors of small molecules and catalytic systems on the basis of mixed porphyrin-containing complex compounds” in the frame of the program of fundamental research RAS №8P “Direct synthesis of  substances with given properties and creation of  functional materials on their basis”.
 
Group leader: Lomova Tatiyna Nikolaevna, Doctor of chemical sciences , Professor
 
Major research problems:
Synthesis of mixed complexes of transition metals, containing porphyrin ligands with various degree and nature of substitution, quantitative research of the reactions of  converted addition of inorganic molecules (water, oxygen, hydrogen peroxide) and small molecules of organic bases, catalytic redox-reactions and obtaining new effective receptors and catalysts on the basis of these data.                        
 
Current state of researches:
Development of optimal techniques of the synthesis of symmetric and asymmetric acidoporphyrin substituted complexes of higher-charged cations of metals on the basis of general method of synthesis of acidoporphyrin complexes apply stable compounds of higher charged metals cations, excluding preliminary obtaining unstable salts of double-valent metals as classical complex-agents in chemistry of porphyrins had been performed. Complexes displaying important catalaze activity in water-organic media in the presence of alkali will be founded by means of modification of the composition of mixed coordinative spheres, functional substituents and nature of coordinative interactions, and ion-molecular and radical mechanisms of decomposition, including, as supposed, stages of coordination of peroxide by metalloporphyrin and ox-red in terms of aromatic macrocycle will be explained. Various structure of organic part of the catalyst will be used for regulating catalaze activity of the complexes.
  
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Subject: “Structure, chemical reactions mechanisms, reactivity of higher-substituted porphyrins and synthesis of functional materials on their basis” (State registration  № 0120.0 511046)
 
Group leader:   Lomova Tatiyna Nikolaevna, Doctor of chemical sciences , Professor
 
Major research problems:
Problems of structural-functional study of porphyrins in solutions and mechanisms of their chemical and photochemical conversions is important for studing the processes lying in the basis of biological processes. At present, similar investigations are carried out all over the world.  The aim of the laboratory is to research directed synthesis of symmetric and asymmetric substituted porphyrins with new unique properties, such as low ox-red potentials, coordinative unsaturation in combination with high stability, kinetics and mechanisms of reactions involving synthesied porphyrins, such as transfer reactions of small molecules, formation and dissociation of their complexes, ox-red and photochemical reactions, catalytic processes.
 
Current state of researches:
At present, general results on the models of synthetic tetraphenilporphyrin and phthalocyanine were obtained. The reactions of conversed transfer of electrons and small molecules, including components of atmospheric air (oxygen, nitrogen) and toxic hydrogen sulphide, were studied. Fundamental characterizations of rate and equilibrium constants of unconversed and conversed reactions were obtained, complicated multistaged mechanisms of the processes, transitional states and stable intermediates were established, paramount role of the solvent and products of interaction of participants of the chemical reactions with it was shown, correlation of parameters of reactions with physicochemical constants of solvents and their chemical nature were found. In the course of the study new numerous problems of reactivity of liquid systems with porphyrin components were set. 
 
The results of investigation of applied properties of porphyrins solutions is the development of the catalysts of the homogenic and geterogenic processes (electroreduction of oxygen, photosensibilization and dezactivation of oxygen), of stabilizators for polymeric materials, components membranes for separating natural gases mixtures and converters of sun energy. This development obtained the prize of Government of Russian Federation. The results were repeatedly reported at the international conferences in the field of the considered problem; their correspondence to the world level is out of doubt.   
 
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Topic: Porphyrinates of precious metals.  Synthesis and investigation of coordinative and applied properties, carried out according for the grant RNRF № 06-03-96343
 
Group leader: Lomova Tatiyna Nikolaevna, Doctor of chemical sciences , Professor
 
Major research problems:
To obtain mixed acidoporphyrin complexes of metals of group 8  of the Periodic System and silver and gold, to establish their structure, to study stability, electron-optic and electrophysic properties and to search compounds with high concentration of mobile carriers charge, which are  optimal for applying in optoelectronics of electronic spectrum among synthesised complexes. The complexes with coordinative unsaturational central atom of precious metal will be obtained as perspective catalysts of ox-red reactions.
 
Current state of researches:
Fundamental task of research topic is the problem of world science, designs for obtaining complexes with porphyrins and their commercial application activity are performed in research centres of  Europe, USA and Japan. In the laboratory there is a “monopoly” on complexes with synthetic porphyrin-tetraphenylporphyrin. In the world science octaethylporphyrin or phthalocyanine are usually used. Tetraphenylporphin, in spite of the similarity of general macrocycle with the mentional porphyrins applied abroad, present quite different coordinative chemistry because of special corrugated structure and presence of electronic deficit in the macrocycle. Consequently, synthesis of complexes with this porphyrin is highly perspective for obtaining components of new materials for optoelectronics and catalysis. 
 
The methods of the synthesis were developed in the laboratory and coordinative and applied properties of porphyrin complexes, more simple in comparison to the complexes with precious metals structure, were investigated. There are original methods of synthesis of complexes of tetraphenylporphyn with higher-charged  cations of metals from available compounds of metals in stable degrees of oxidation, defended by authors’ certificates (usually abroad, according to literature data for synthesis, reductional unstable initial compounds of metals are used). The materials of the research were presented at all four international conferences on porphyrins and phthalocyanines (Digon, Ciuoto, New Orleans, Rome).
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Topic: Complexes manganese with substituted porphin, porphirazin and phthalocyanine as perspective models of natural catalases carried out according to the Grant of President RF MK-531. 2006. 03.»
 
Group leader: Kiseleva E. N. , PhD, Researcher 
 
Major research problems: 
Direct synthesis of new manganese (3) complexes with functionaly substituted porphin, porphyrazin and phthalocyanine and investigation of their coordinative and catalytic properties, foundation of mechanisms of catalase action.
 
Current state of researches:
Synthesis was performed, structure of manganese (3) complexes with substituted by means of various tetrapyrrol macrocycles was established and data on their reactivity and mechanisms of dissociation reactions in the media acids, ox-red under the action of peroxide hydrogen in neutral solutions were obtained. Results of the investigations allows to realize practical application of manganese-porphyrins as the models of the catalysts and conversed transfer of small organic and inorganic molecules in natural fermentative processes.
 
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Topic: “Chemically stability and catalytic properties of manganese (3) porphyrins with various type of substituents in aromatic macrocycle”, carried out according to the out-departmental research program “Development of research potential of higher school”, Subprogram №3 “Development of  infrastructure of research-technical and innovational activity of higher school and its staff potential”, Section № 3, 5 “Research carried out by junior researchers and teachers  in the large research-educational centres, including abroad, including participation at the conferences, simposiuma, seminars, school, including abroad.
 
Group leader: Kiseleva E. N. , PhD, Researcher
 
 Fundamental problems:
Obtaining of manganese derivatives of substituted porphyrins and investigation of their state in the solvents of various nature, reactivity on  relation to acids and catalytic activity in the model reaction of disproportionation of peroxide hydrogen.
 
Current state of researches:
Synthesis of manganese (3) porphyrins with various structure of macrocycle and identification of synthesied compounds was performed,  their chemical nature and composition were confirmed by physico-chemical and chemical methods such as qualitative and quantitative analyses, extra-violet and infrared spectroscopy, NMR spectroscopy, mass-spectroscopy, roentgen-structural analysis.
Awards:

 

  • Metalloporphyrins as catalysts and chemical reagents – Bronze Medal of  Exhibition of National Economy Achievements (ENEA); 
  • Prize of Russian Federation Government in the field of Science and Engineering 2002; 
  • Support of grant RAS, Ministry of Education of Russian Federation; President of  Russian Federation, Russian National Research Foundation, Foundation of Assistance of National Science.