Metal-Imidazole, Metal-Imidazoline and Post-Modified Metal-Imidazolium Aggregates for C-C Bond Formation Reactions

Chatla, Naga Babu (2016) Metal-Imidazole, Metal-Imidazoline and Post-Modified Metal-Imidazolium Aggregates for C-C Bond Formation Reactions. PhD thesis, Indian Institute of Technology Hyderabad.

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Abstract

Construction of functionalized coordination polymers (FCPs) have been the subject of interest in last few decades due to their fascinating architectures and versatile applications in catalysis, gas storage, separation, luminescence, electrical conductivity, magnetism, and nonlinear optics. The suitable organic spacers, metal precursors and synthetic methodologies are the essential criteria to design the FCPs with different physical properties. Therefore, the choice of organic spacer is extremely important to fine-tune the structural and desired functional properties of FCPs through coordination mode or non-covalent interaction mode. Among different types of organic spacers, the imidazole/imidazolium/imidazoline types of ligands are of special interest as they have potential functional group for pre/post modification along with excellent functional group tolerance at N-positions. Imidazole and their salts in particular comprise a boundless and emerging field. The unique structural feature of imidazole ring with desirable electron-rich characteristic is beneficial for imidazole derivatives to readily bind with a variety of metals and associates through diverse weak interactions, thereby exhibiting broad structural diversity. In particular, the imidazolium salts enable many emerging applications including catalysis, nanocomposites, and CO2 absorbents. Particularly, numerous imidazole and their derivatives have been extensively used in the coordination chemistry to generate various types of applications with high potency, which have shown the enormous development value. Thus, the thesis dealt (i) the design, synthesis and characterization of new imidazole/imidazoline/imidazolium carboxylic acid organic spacers, (ii) synthesis and characterization of novel imidazole/imidazoline/imidazolium carboxylate based coordination polymers, (iii) structural diversity and close interracial relationships between main group and transition metal imidazolium carboxylate based coordination assemblies. A thorough literature survey on imidazolium carboxylate coordination polymers (till March 2016), seven new imidazolium carboxylate organic spacers along with their eighteen new synthetically intriguing metal aggregates and their catalytic activities in carbon-carbon bond formation reactions have been reported in the thesis. These new molecules have been fully characterized.

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