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Macroheterocyclic ligands on polymers

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Host Guest Complex Chemistry III

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 121))

Abstract

Macroheterocyclic ligands of the crown ether and cryptand type have proven to be versatile complexing agents for a variety of ionic and neutral solutes. When bound to a macromolecular chain, their binding properties can change significantly as a result of cooperative binding effects involving adjacent ligands or comonomer substituents, microenvironmental effects caused by the polymer backbone or by neighboring groups, conformational restrictions imposed upon the macrocyclic ring due to the close proximity of other polymer-bound entities, interaction between the bound solutes, etc. In this respect, soluble polymeric crown ethers and cryptands can serve as excellent model compounds for studying solute binding to neutral macromolecules in both aqueous and non-aqueous systems. The effect of variables such as distance between bound macrocycles, length and structure of spacer between bound ligand and polymer backbone, flexibility of the polymer backbone and ionic or neutral comonomer substituents can be determined by a variety of techniques, both in catalytic and solute binding applications. The behavior of certain poly(crown ether)s in water is especially of interest for a better understanding of the binding of monomeric and polymeric solutes to neutral and charged polysoap-type macromolecules.

The knowledge acquired from the soluble polymeric systems is necessary in unraveling the often more complex phenomena encountered with immobilized macroheterocyclic ligands. The latter, of course, are of interest in chromatographic separations, phase-transfer catalysis and other applications where their insolubility or ease of recovery is required. The effect of network swelling, crosslink density, particle size, site accessibility, porosity and other network parameters are not always well understood, and more quantitative work with both linear and network polymeric macroheterocyclic ligands is needed. Although commercial application may at present be limited by economic considerations, the immobilized macrocycles nevertheless can function as very valuable compounds to study the characteristics of solute binding to network structures, and are also useful in studying interactions between solutes and soluble ligands in low polarity media.

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Smid, J., Sinta, R. (1984). Macroheterocyclic ligands on polymers. In: Vögtle, F., Weber, E. (eds) Host Guest Complex Chemistry III. Topics in Current Chemistry, vol 121. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-12821-2_4

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  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-12821-2

  • Online ISBN: 978-3-540-38750-3

  • eBook Packages: Springer Book Archive

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