Supramolecular Cation Coordination Chemistry

The study of supramolecular complexes of metal cations is really nothing more than the coordination chemistry of relatively labile (i.e. ligand substitution is relatively rapid under ambient conditions) metal ions and relatively elaborate, usually chelating or multidentate ligands (see Section 1.5) T It is therefore worth spending a little time reviewing some basics of coordination chemistry before looking at specific supramolecular systems. Experts read no further ... 

Supramolecular chemistry involves a generalisation of the principles of coordination chemistry and was first applied to hosts for metal cations. 

The great impact in metal-ion coordination chemistry caused by the discovery of the macrocyclic polyethers31 has led to new designs of chemosensors for the alkali cations. Application of a supramolecular receptor to fluorescence sensing was first... 

Figure 5.28 The two-dimensional supramolecular network in [RE(NMP)4(H20)4][H cGeMoi204o] [79]. (Reprinted with permission from H. Zhang, et al., Synthesis, crystal structure, and photochromism of novel two-dimensional supramolecular networks based on Keggin-type polyoxoanion and lanthanide coordination cations, Inorganic Chemistry, 42, no. 24, 8053-8058 (Figure 3), 2003. 2003 American Chemical Society.)...

For a number of years the research interests of the Beer group have covered many areas of macrocychc coordination and supramolecular chemistry. This article reviews our latest results of current research by focusing on three major sections sensing of cations and anions anion templated assembly of pseudorotaxanes and rotaxanes, and metal-directed self-assembly using the dithiocaibamate ligand. 

Meanwhile, cation - crown complexes were fully optimized by ab initio QM techniques in the gas phase, allowing to investigate the effect of electronic reorganization (mainly charge transfer + polarization effects) on the recognition properties/15,161 QM/MM hybrid methods which combine a QM representation of the ion coordination sphere with a MM representation of the more remote species, have been tested on 18C6/ cation complexes/17, 18] Typical applications of "computational approaches in supramolecular chemistry" up to 1994 can be found in ref. [191 There are also reviews on more specialized fields like calixarenes/20,21]... 

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