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By J. D. Dunitz

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However a given selectivity may be increased by structural modifications. For instance the K+/Rb + selectivity increases markedly from 80 to 86. Indeed the introduction of the benzo ring is expected to decrease the cavity size (shorter 0 . . 0 distance) and to increase ligand rigidity (rotation about the central C--C bond in the benzo bridge is frozen). Both effects hinder the cavity dilatation required for Rb + inclusion; on the other hand, they also favour the smaller Na + cation with respect to K+, thus diminishing the K+/Na + selectivity of 36 as compared with 80.

Complex formation of ligand 46 with K +, Na+, Li+ and Ca++ has been reported (92). 40 Design of Organic Complexing Agents. Strategies towards Properties a) b) Fig. 7. Crystal structure and conformation of a) its RbSCN cryptate (from Ref. 3. -M. Lehn with kf, ka = rates of formation and dissociation respectively. The thermodynamic stability constant Kt~ is given by: /c[L, M-+] Ktn -- IT, ELI/~ EM-+] (xI) where It, ]L, ]• are the activity coefficients for the three species; since these are generally unknown the reported quantities are concentration stability constants Ks Ks = Kth ]L ]~t [L, Mn+] ]c -- [L] (XlI) The Ks values correspond to a given conformation of the solvated ligand (L)solv which m a y or may not remain the same in the complex; in some cases several conformations m a y be imagined (see Fig.

Strategies towards Properties but macrobicyclic hgands, which shield the cation more efficiently, only give ligand separated ion-pairs (745). 10. Cation Transport. Design of Selective Cation Carriers Organic Hgands forming AC complexes may be able to induce cation transport through artificial or natural membranes. Since this topic is treated in detail in other chapters of this volume (see pp. 126ff, 152ff) ; the present brief discussion will be limited to synthetic ligands. Although several mechanisms may be envisaged, the transport process via a cation carrier presents three main steps: formation of the complex between the carrier molecule and the cation; dissolution and diffusion of the complex in the membrane; release of the cation from the carrier.

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Alkali Metal Complexes with Organic Ligands by J. D. Dunitz

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