Crown ethers, cation binding

Figure 12 Crown ether-cation binding modes (a) good fit (b) perching (c) sandwich (d) small cation (e) multiple cations.

Number of donor atoms. In general, supramolecular interactions are additive, hence we would expect the larger crown ethers to bind more strongly to metal cations as long as all of the donor atoms can fit around the metal. This contributes to the plateau selectivity seen for most cations on the right-hand side of Figure 3.20. 

Incidentally, C. J. Pedersen s first report on crown ethers and their complexes was published in the same year as the mechanism of the biological activity of valinomycin was clarified [2], Crown ethers are cyclic derivatives of polyethylene glycol of varying ring size, an example of which is also depicted in Figure 2.2.1. The structural relationship with the ionophores is clearly visible. It is thus not surprising that crown ethers also bind metal cations by coordination with the oxygen atoms [1, 3]. 

Moreover, intermacromolecular complex formation is applied to selective recovery of organic and metallic ions. For example, as shown in Table 27, Cu2+ ion is much more effectively precipitated by the polyelectrolyte complex than by one of its components520. Furthermore, polyelectrolyte complexes including some metal ions have been studied in recent years (see Sect. 3.2.). Crown ethers can bind certain cations they especially exhibit high affinity to K+. Smid et al.S21) synthesized poly(vinylbenzo-[18]-crown-6). Such polymers containing crown ether with K+ behave like polycations in solution and can interact with polyanions such as poly(carboxyHc acid) to generate a kind of polyelectrolyte complexes. Moreover, PAA may interact with the ether oxy-... 

The tren-based heteroditopic receptor 22, featuring a tripodal tetrahedral amide hydrogen-bond anion-recognition site in combination with benzo-15-crown-5 ether cation-binding moieties, has been found to cooperatively bind chloride, iodide, and perrhenate anions via co-bound crown ether-complexed sodium cations. It also can efficiently extract the radioactive sodium pertechnetate from simulated aqueous nuclear waste streams. The anion-binding affinity of 22 is considerably reduced in the absence of a co-bound cation <1999CC1253>... 

Figure 11.5 Crown ether cyclophane binds squaraine dye only in the presence of sodium cations...

Covalent binding of an anion and a cation receptor to obtain a ditopic receptor and subsequent application in an SLM has been reported by Rudkevich et al. (66). They synthesized a receptor (carrier 14) which is capable of binding a cation and an anion simultaneously. The crown ether part binds Cs, while the salophene moiety can complex Cl. For carrier 14 CsNOj-fluxes (J = 0.89 x 10 mol m s ) and CsCl-fluxes (J = 1.2 X 10 mol m s ) were measured. In the case of cation assisted transport, CsNOj is expected to give a higher flux than CsCl, due to the higher lipophilicity of the NO3 anion. This proves that both the anion and the cation are involved in the complexation of CsCl, and that selective transport of a hydrophilic salt over a lipophilic salt can be obtained with a ditopic receptor. 

Almost as soon as Pedersen announced his discovery of the crown ethers (see Chaps. 2 and 3) it was recognized by many that these species were similar to those prepared by Busch and coworkers for binding coinage and transition metals (see Sect. 2.1). The latter compounds contained all or a predominance of nitrogen and sulfur (see also Chap. 6) in accordance with their intended use. The crown ethers and the polyazamacrocycles represented two extremes in cation binding ability and preparation of the intermediate compounds quickly ensued. In the conceptual sense, monoazacrowns are the simplest variants of the macrocyclic polyethers and these will be discussed first. 

In Pedersen s early experiments, the relative binding of cations by crown ethers was assessed by extraction of alkali metal picrates into an organic phase. In these experiments, the crown ether served to draw into the organic phase a colored molecule which was ordinarily insoluble in this medium. An extension and elaboration of this notion has been developed by Dix and Vdgtle and Nakamura, Takagi, and Ueno In efforts by both of these groups, crown ether molecules were appended to chromophoric or colored residues. Ion-selective extraction and interaction with the crown and/or chromophore could produce changes in the absorption spectrum. Examples of molecules so constructed are illustrated below as 7 7 and 18 from refs. 32 and 131, respectively. 

A good deal of work has been done on polymeric crown ethers during the last decade. Hogen Esch and Smid have been major contributors from the point of view of cation binding properties, and Blasius and coworkers have been especially interested in the cation selectivity of such species. Montanari and coworkers have developed a number of polymer-anchored crowns for use as phase transfer catalysts. Manecke and Storck have recently published a review titled Polymeric Catalysts , which may be useful to the reader in gaining additional perspective. 

It was noted early by Smid and his coworkers that open-chained polyethylene glycol type compounds bind alkali metals much as the crowns do, but with considerably lower binding constants. This suggested that such materials could be substituted for crown ethers in phase transfer catalytic reactions where a larger amount of the more economical material could effect the transformation just as effectively as more expensive cyclic ethers. Knbchel and coworkers demonstrated the application of open-chained crown ether equivalents in 1975 . Recently, a number of applications have been published in which simple polyethylene glycols are substituted for crowns . These include nucleophilic substitution reactions, as well as solubilization of arenediazonium cations . Glymes have also been bound into polymer backbones for use as catalysts " " . 

The bulk of the work which has been performed on open-chained crown ether and cryptand equivalents, especially for application to general cation binding studies has been accomplished by Vogtle and his coworkers. Vogtle has reviewed both his own and other work in this field . 

In later work, Vogtle and his coworkers prepared analogs of both crown ethers and cryptands. These molecules are designed to have a terminal donor group which is capable of offering a complexed cation additional binding sites. Numerous... 

Alcohols can be selectively bound to the same host type if they are combined with an amine and vice versa, considering that a cation and an anion will be formed through a proton transfer. The so-formed alkoxide anion will bind to the boron atom, while the ammonium ion will be complexed by the crown ether (147, Fig. 39). Competition experiments involving benzyl-amine have shown enhanced selectivity for the complexation of alcohols with... 

---