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The study of macrocyclic coordination compounds and with open outline of some metals based on 2,6-diformilthiofenolate


Author: Lozan Vasile
Degree:doctor habilitat of chemistry
Speciality: 02.00.01 - Inorganic chemistry
Year:2021
Institution: Institute of Chemistry of the ASM

Status

The thesis was presented on the 20 January, 2021 at the meeting of the Scientific Council and now it is under consideration of the National Council.

Abstract

Adobe PDF document2.01 Mb / in romanian

Thesis

CZU 546.55-3.06(043.2)

Adobe PDF document 7.54 Mb / in romanian
307 pages


Keywords

macrocyclic compounds, supramolecular chemistry, crystalline structure, transition metals and non-transition metals

Summary

The dissertation consist of introduction, 6 chapters, conclusions and recommendations, 422 references, 307 pages integrally, 179 figures and 6 annexes. The obtained results are presented in 32 scientific articles and 10 abstracts at conferences.

The purpose and objectives of the thesis is to develop effective methods of synthesis of new macrocycles dithiophenolate ligands and all-round study of complexing processes of metals as well as investigation of reaction in the cavities of synthesized macrocyclic complexes; to investigate structural and steric regularities of formation reactions of complexes macrocycles as well as the modes of coordination, the conformations of macrocyclic ligand and co-ligands; to esta-blish the influence of structural, steric and electronic factors on the processes of formation of macrocyclic complexes with metals.

Novelty and scientific originality. Original methods have been developed for the synthesis of macrocyclic complexes of 3d-transition metals and some non-transition metals with open cavities. Structural and steric regularities of formation reactions of macrocyclic complexes have been determined. It was established that macrocyclic complexes cavities give unusual ways of coordination or special conformations of coligands, stabilize unstable reagents, form tetra-nuclear compounds with various bridges (S62¯, anions with carboxylate and azole groups) and demonstrated that formation of tetranuclear clusters criticaly depends on the length of bridging coligand and steric requirements of the macrocyclic ligand. It was demonstrated the selectivity of bromination reactions in the macrocyclic cavity in order to obtain the stereoselectively bromi-nated and the charge-transfer compounds. For the first time it has been synthesized three- and pentanuclear macrocyclic compounds having as bridge ferrocene-carboxylate groups, resulting in a large shift in the redox potential of the ferrocenyl center demonstrating that the transfer of electrons to the rest of the ferrocenyl and binuclear subunits influence each other.

Based on the obtained fundamentally new results to science and practice it has been identified a new direction in the coordination chemistry through elaboration of original synthesis methods of a new class of hexaazadithiophenolate macrocyclic ligands as well as its macrocyclic complexes of metals. These compounds are the first prototypes of polynuclear molecules containers. The synthesized coordination compounds are the first representative of a new class of complexes in which are combined the macrocyclic coordination complexes with various organic and organometallic compounds that present an increased interest for applications in analytical and organic chemistry as well as in the industry.

The practical values of the work. New efficient methods of synthesis of hexaazadithiopheno-late macrocyclic ligands and their derivatives, as well as macrocyclic coordination compounds based on them were developed. Based on bromination reaction in cis-position of α, β-unsaturated carboxylate in cavity of complexes a new stereoselective synthesis method has been developed. Fixation of CO2 by macrocyclic complexes might be of great importance in biological processes, technological and environmental protection. The compounds with charge transfer, which adsorb I2, may be used as adsorbents for storage, detection and slow elimination of iodine.