Cationic guests

FIGURE 6-15 Schematic representation of the ion permeability modulation for cation-responsive voltammetric sensors based on negatively charged lipid membranes. Complexation of the guest cation to the phospholipid receptors causes an increase of the permeability for the anionic marker ion. (Reproduced with permission from reference 49.)... 

Solutions were 2 x 10-3 mol dm-3 in compound, and potentials were determined with reference to the SCE, b Three-electron reversible oxidation process. Two-electron reversible oxidation process. Separation between anodic and cathodic peak potentials values for ferrocene under identical conditions ranged from 80 to 90 mV. Shift in respective ferrocenyl oxidation potential produced by presence of guest cation (2 equiv) added as their thiocyanate salts for potassium and ammonium, and their picrate salts for methylammonium and phenethyl-ammonium. 

The electrochemical properties of [59]—[66] in the presence and absence of stoichiometric amounts of Na+ and K+ guest cations were investigated in... 

The guest cations hitherto examined cover broadly uni- to trivalent and inorganic to organic ions that include alkali, alkaline earth, heavy and transition metal ions, as well as (ar)alkyl ammonium and diazonium ions. As to the complex stoichiometry between cation and ligand, both 1 1 stoichiometric and 1 2 sandwich complexes are analyzed. The solvent systems employed also vary widely from protic and aprotic homogeneous phase to binary-phase solvent extraction. 

Fig. 1. The inclusion of a pentamethylene-diammonium guest cation in an uncharged cryptand 51 a formula, b crystal structure...

Size match between host cavity and guest cation. In fact, the flexible [18] crown-6 is a reasonably good size match for all of the alkali metal cations, although it is optimum for K+. 

D. Electrochemical Recognition of Transition Metal Guest Cations by Ferrocene Aza-, Thia-Donor Macrocyclic Ligands... 

We have recently prepared a new chromophoric and redox-responsive ionophore (4) containing a tricyanovinyl redox-active moiety (35) (Scheme 2). Electronic absorption spectra of (4) exhibit hypochromic shifts on binding Group IA and IIA metal cations and cyclic voltamme-tric electrochemical investigations reveal that (4) electrochemically recognizes Na+ and K+ guest cations, resulting in one-wave CV shifts of the tricyanovinyl reduction wave (80 and 20 mV, respectively) to more anodic potentials. 

Although a selection of ferrocene crown ethers (Scheme 4) were initially reported by Biernat and Wilczewski (44), Saji (45) described the first evidence of anodic shifts in the oxidation potential of pentaoxa[13]-ferrocenophane (6) resulting from the addition of alkali metal salts. Two distinct electrochemical CV waves corresponding to complexed and uncomplexed (6) were observed for both Na+ and Li+ guest cations (Fig. 4). The respective anodic shifts correspond to a decrease of the... 

A number of ferrocene cryptand molecules (66-74) ((29)—(31)) have been reported in the literature and it is only relatively recently that their electrochemical coordination properties have been disclosed. We have synthesized potassium-selective metallocene cryptands (72) (30) and (31) the electrochemistry of the former in the presence of K+ guest cations proved disappointingly irreversible (75). Hall and co-workers (76) have used cyclic voltammetry to investigate the coordination of... 

The electrochemical properties of (40)-(47) in the presence and absence of stoichiometric amounts of Na+ and K+ guest cations were investigated in acetonitile solution by cyclic voltammetry. Table VI shows that addition of alkali metal salt in 1 1 molar ratio produces anodic shifts (AE) in the original redox couple of 40-320 mV in the reduction potentials of the respective host s molybdenum redox center. Comparing (45)-(47) with the organic redox-active quinone systems described earlier (see Table I), in the case of Na+ guest cation these AE... 

Novel heterotrinuclear complexes ((64), (65)) have also been described by the same group (107), although no electrochemical recognition studies of Group IA, IIA guest cations are reported. 

Besides the ferrocene crown ether ligands described earlier, a variety of related macrocyclic ferrocenophanes containing various sulfur, oxygen, and nitrogen heteroatoms have been reported by a number of groups (110-115) (Scheme 21). These ligands complex transition metal guest cations such as Ag(I), Cu(I), and Pd(II) (116,117). Of particular... 

Gokel for reducible quinone (25, 26) and nitroaromatic (32, 33) lariat crown ethers with alkali metal guest cations discussed earlier. Support for the latter effect comes from the related ligand system (81), containing no amide carbonyl groups, and electrochemical results revealing... 

---