Structural organization macromolecular metal complexation

This book provides an overview of possible combinations of metal complexes and metals with organic and inorganic macromolecules (often also named macromolecular metal complexes — MMC [1]). This book covers the formation, synthesis, structure and properties of these exciting and relatively new materials. Metal-containing macromolecules are a fascinating field of science. It is readily understandable that materials with unusual properties are obtained by having a metal complex or metal as part of a macromolecule. Nature shows us the functions of such materials extremely well by the selectivity and activity of, for example, hemoglobin, photosynthesis and metalloenzymes. 

Kinetics and Thermodynamics of Formation of Macromolecular Metal Complexes and Their Structural Organization... 

Used widely in synthetic macromolecular and natural biopolymer fields to evaluate structural and thermodynamic properties of macromolecular materials, thermal analytical methods have been applied to assist in the characterization of natural organic matter (NOM). Originally applied to whole soils, early thermal studies focused on qualitative and quantitative examination of soil constituents. Information derived from such analyses included water, organic matter, and mineral contents (Matejka, 1922 Tan and Hajek, 1977), composition of organic matter (Tan and Clark, 1969), and type of minerals (Matejka, 1922 Hendricks and Alexander, 1940). Additional early studies applied thermal analyses in a focused effort for NOM characterization, including structure (Turner and Schnitzer, 1962 Ishiwata, 1969) and NOM-metal complexes (e.g., Schnitzer and Kodama, 1972 Jambu et al., 1975a,b Tan, 1978). Summaries of early thermal analytical methods for soils and humic substances may be found in Tan and Hajek (1977) and Schnitzer (1972), respectively, while more current reviews of thermal techniques are provided by Senesi and Lof-fredo (1999) and Barros et al. (2006). 

The results obtained show that immobilization of metal complexes in polymer gels allows to prepare physically heterogeneous and chemically homogeneous catalysts and leads to an important increase in their activity, selectivity and stability in the reactions of dimerization of lower olefins. The immobilization of the complexes opens new possibilities of macromolecular design of the catalysts with desired structural organization and will contribute to the development of general principles of synthesis of highly efficient and environmentally friendly catalytic systems for liquid phase processes. 

There are three major databases storing all the crystal structures determined so far the CSD (Cambridge Structural Database) contains all the organic and metal-organic compounds the ICSD (Inorganic Crystal Structure Database) contains the inorganic compounds and the PDB (Protein Data Bank) contains macromolecular structure data on proteins, nucleic acids, protein-nucleic acid complexes, and viruses. 

As far as electron transfer properties directly involving dendrimers are concerned, it can be generally considered that these reactions may be observed whenever the macromolecular structure contains one or more units featuring redox levels at accessible potentials. The first dendrimers prepared were purely organic macromolecules, with no unit appropriate for electron transfer reactions. Later, however, the introduction of metal and organometallic complexes in the dendritic structure opened new possibilities to the chemistry of dendrimers. Indeed, the incorporated metal units exhibit important properties such as absorption and emission of visible light (relevant for the construction of antenna systems see Volume V, Part 1, Chapter 7) and redox levels at accessible potential, which are necessary for electron transfer reactions. Successively, purely organic electroactive units have also been used to functionalize the dendrimers. 

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