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Molecular design, synthesis and X-ray study of zero-dimensional and polymeric coordination compounds based on dioximes with Cu(II), Zn(II) and Cd(II) transition metals


Author: Croitor Lilia
Degree:doctor of chemistry
Speciality: 01.04.18 - Crystallography and crystallophysics
Year:2012
Scientific adviser: Marina Fonari
doctor, associate professor (docent), Institute of Applied Physics of the ASM
Scientific consultant: Eduard Coropceanu
doctor, professor, Institute of Chemistry of the ASM
Institution: Institute of Applied Physics of the ASM
Scientific council: DH 02-01.04.18
Institute of Applied Physics of the ASM

Status

The thesis was presented on the 26 September, 2012
Approved by NCAA on the 15 November, 2012

Abstract

Adobe PDF document1.68 Mb / in romanian

Keywords

crystallography, coordination chemistry, coordination polymers, α-dioximes, adsorption properties, luminescent materials.

Summary

The thesis includes 142 pages and consists of introduction, three chapters, conclusions and recommendations, 231 bibliography sources, 9 tables, 57 figures and 5 annexes. The obtained results were summarized in 24 publications. Keywords: crystallography, coordination chemistry, coordination polymers, α-dioximes, adsorption properties, luminescent materials.

Research field: 01.04.18 – Crystallography and crystal physics. The purpose of the dissertation: the synthesis and X-ray investigation of novel coordination compounds with adsorptive and luminescent properties. Objectives: to design new mixed-ligand coordination compounds based on Cu(II) dioximates and Zn(II) and Cd(II) dioximes; to identify the differences in coordination modes of α-dioximes to d9 Cu(II) cation and d10 Zn(II) and Cd(II) cations in the presence of 4,4'-dipyridyl bridging type ligands; to study factors responsible for the dimensionality of new coordination compounds and their application for diversification of objects of the research; to evaluate by theoretical and experimental methods the possibilities to use the new complexes as adsorption materials; to examine luminescent properties of obtained compounds in order to find new photosensitive materials.

Scientific novelty: For the first time the binuclear Cu(II) dioximates mediated by dipyridine type ligands and mono-, bi- and polynuclear Zn(II) and Cd(II) dioximes were synthesized and their crystal structures were determined by single-crystal X-ray method. It has been shown that the coordination of bulky dioxime molecule to the metal center results in the loosely packed crystals, which are characterised by the presence of intermolecular cavities where the molecules of „guest” type can be enclathrated. For the first time the investigation of the luminescent properties of such type compounds has been carried out.

Important scientific problem solved: For the first time have been synthesized and investigated zero-dimensional and polymeric compounds of Cu(II), Zn(II) and Cd(II) on the base of α-dioximes with “wheel-and-axle” topology, that are characterized by the presence of intermolecular cavities and can encapsulate the „guest” molecules.

Theoretical significance:The results of this study make a significant contribution to the chemistry of coordination compounds. It has been demonstrated that the bulky and stable metal-oxime ”building block” is utilized successfully in the design of new coordination polymers with useful properties.

Practical significance: Methods of synthesis of Cu(II) dioximates and Zn(II) and Cd(II) dioximes; fluorescent emission points to the possibility of using these compounds as photosensitive materials.