Synthesis and complexing properties of bis-crown ethers incorporating benzo-15-crown-5 and metallocene

Bis-crown ethers in which the benzo-15-crown-5 units were linked to 1,1′-positions of metallocene (M = Fe or Ru) with amide, ester, or ? C? C? bonds were synthesized. Complexing ability of the compounds with alkali, alkali earth, and transition metal cations were measured by the solvent extraction method. The results showed that these crown ethers had high affinity toward alkali metal cations (Li⁺, Na⁺, K⁺, and Rb⁺) and heavy-metal cations (Ag⁺ and Tl⁺). The difference of complexing ability for metal cations between ferrocene and ruthenocene derivatives could not be detected significantly. The extractability of metallocene-bis-crown ethers for metal cations was more larger than that of the corresponding mono-crown ethers, and irregular increments of extractability were explained by assuming the existence of a mixture of 1:1 and 2:1 complexes.     

Synthesis,alkali metal picrate extraction,and alkali metal cation binding selectivities of some new cage‐annulated polyoxamacrocyclic crown ethers

Five new cage‐annulated crown ethers, i.e., 4a, 4b, 6b, 11a, and 11b, have been synthesized and their respective alkali metal picrate extraction profiles along with that of a previously synthesized host molecule, 6a, have been obtained. These results are compared with the corresponding results obtained for electrospray ionization mass spectrometric (ESI‐MS) measurements of relative binding selectivities displayed by the same hosts toward a series of alkali metal chlorides. Among the crown‐5 hosts studied, 6a displays enhanced avidity toward complexation with K⁺ picrate in liquid‐liquid extraction experiments. Among the three crown‐6 hosts, 4b proved to be the best alkali metal picrate extractant and displayed significant levels of avidity toward complexation with the larger alkali metal cations (i.e., K⁺, Rb⁺, and Cs⁺). The trends in the picrate extraction and the ESI‐MS results obtained herein show several notable similarities and some differences. The similarities generally stem from size‐selective binding properties that are intrinsic to the different cavity sizes of the cage‐annulated macrocycles, whereas the differences reflect the important influence of solvation effects on the binding properties of the macrocycles.     

Spectrophotometric studies of alkali and alkali earth metal ions complexes of mono amino derivative of calix[4]arene

The synthesis and complexive abilities of 5,11,17-tris(tert-butyl)-23 amino-25,26,27,28-tetra-propoxycalix[4]arene towards alkali cations Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and alkali earth cations Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ in methanol-chloroform mixture have been evaluated at 25°C, using UV-Vis spectrophotometric techniques. The results showed that the ligand is capable to complex with all the cations by 1: 1 metal to ligand ratios. The selectivity presented considering the calculated formation constants are in the order Li⁺ > Na⁺ > K⁺ > Rb⁺ > Cs⁺ and Mg²⁺ > Ca²⁺ > Sr²⁺ > Ba²⁺ with the ligand.     

Cation-binding properties of poly- and bis(benzo-21-crown-7)derivatives

Summary Poly- and bis(crown ether)s which contain the relatively large crown ether ring of benzo-21-crown-7 were synthesized, and their cation-binding properties for alkali metal cations were elucidated by solvent extraction and also conductometrically. The cation-binding ability was found to decrease in the order Cs⁺>Rb⁺>K⁺>Na⁺. They can extract alkali metal cations more efficiently than the corresponding monomeric analogue. The binding behaviour for some organic cations such as alkyl ammonium and guanidinium is also described.

---

Kationen-Bindungsvermögen von Poly- und Bis(benzo-21-krone-7)-Derivaten

Zusammenfassung Poly- und Bis-kronenether mit dem relativ großen Kronenetherring Benzo-21-krone-7 wurden dargestellt und ihr Bindungsvermögen für Alkaliionen wurde durch Lösungsextraktion und auch konduktometrisch untersucht. Es ergab sich, daß das Bindungsvermögen in der Reihenfolge Cs⁺>Rb⁺>K⁺>Na⁺ abnimmt. Diese Substanzen können Alkaliionen wirksamer extrahieren als die entsprechenden Monomeren Analogen. Das Bindungsvermögen für einige organische Kationen, wie z.B. Alkylammonium und Guanidinium, wurde ebenfalls untersucht.

     

Selective complexation of alkali metal ions and nanotubular cyclopeptides: a DFT study

A density functional theory based on interaction of alkali metal cations (Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺) with cyclic peptides constructed from 3 or 4 alanine molecule (CyAla3 and CyAla4), has been investigated using mixed basis set (C, H, O, Li⁺, Na⁺ and K⁺ using 6-31+G(d), and the heavier cations: Rb⁺ and Cs⁺ using LANL2DZ). The minimum energy structures, binding energies, and various thermodynamic parameters of free ligands and their metal cations complexes have been determined with B3LYP and CAM-B3LYP functionals. The order of interaction energies were found to be Li⁺ > K⁺ > Na⁺ > Rb⁺ > Cs⁺ and Li⁺ > Na⁺ > K⁺ ? Rb⁺ > Cs⁺, calculated at CAM-B3LYP level for the M/CyAla3 and M/CyAla4 complexes, respectively. Their selectivity trend shows that the highest cation selectivity for Li⁺ over other alkali metal ions has been achieved on the basis of thermodynamic analysis. The main types of driving force host–guest interactions are investigated, the electron-donating O offers lone pair electrons to the contacting LP* of alkali metal cations.     

Synthesis and complexation study of calix[4]arene diamine derivative incorporated in a polymeric backbone with chiral monomers

The novel chiral polymeric compounds containing more than one calix[4]arene have been synthesized by reacting a new calix[4]arene diamine derivative with two chiral monomers. These newly prepared compounds were studied by extraction of toxic heavy metal (Cu²⁺, Co²⁺, Cd²⁺, Hg²⁺), silver and alkali metal (Na⁺, K⁺) cations from aqueous phase. It was observed that the resulting calixarene-based polymers have a good complexing ability towards silver, alkali metal and toxic heavy metal cations.     

Ion transport membranes based on conducting polymers

Polypyrrole membranes containing four different dopant ions were prepared galvanostatically from aqueous solutions of pyrrole (0.1 M) and the appropriate counter ion salt (0.1 M). The transport of mono-valent cations through each membrane was achieved by applying a potential gradient across the membranes. The influence of a number of set up parameters on the flux of K⁺ ions across a PPy/pTS membrane was assessed, as well as the relative selectivities of the four membrane types for the mono-valent cations; Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺.     

A new “switched-on” crown ether which exhibits a reversible all-or-none ion-binding ability

A new photoresponsive crown ether (2) in which the poly)oxyethylene) chain is linked to 4? and 4′-position of azobenzene was synthesized. Trans-(2) completely lacked the affinity to alkali metal cations, while photoisomerized cis-(2) was capable of binding K⁺, Rb⁺, and Cs⁺.     

Synthesis of macrocyclic tetraamides derived from α-amino acids and their investigations using ESI-MS technique

Chiral α,ω-diesters react under high-pressure conditions (10 kbar) with α,ω-diamines to give chiral cyclic tetraamides of C₂-symmetry. The complexation properties of tetraamides towards alkali metal cations (Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺) were estimated on the basis of ESI-MS spectra.     

Determination of orders of relative alkali metal ion affinities of crown ethers and acyclic analogs by the kinetic method

Ladders of relative alkali ion affinities of crown ethers and acyclic analogs were constructed by using the kinetic method. The adducts consisting of two different ethers bound by an alkali metal ion, (M₁ + Cat + M₂)⁺, were formed by using fast atom bombardment ionization to desorb the crown ethers and alkali metal ions, then collisionally activated to induce dissociation to (M₁ + Cat)⁺ and (M₂ + Cat)⁺ ions. Based on the relative abundances of the cationized ethers formed, orders of relative alkali ion affinities were assigned. The crown ethers showed higher affinities for specific sizes of metal ions, and this was attributed in part to the optimal spatial fit concept. Size selectivities were more pronounced for the smaller alkali metal ions such as Li⁺, Na⁺, and K⁺ than the larger ions such as Cs⁺ and Rb⁺. In general, the cyclic ethers exhibited greater alkali metal ion affinities than the corresponding acyclic analogs, although these effects were less dramatic as the size of the alkali metal ion increased.     

Sodium ion sensors based on dibenzo-16-crown-5 compounds with amide side arms

Abstract

Lipophilic dibenzo-16-crown-5 compounds with amide-containing side arms attached to the central carbon atom of the three-carbon bridge in the polyether ring have been applied as neutral carriers for sodium ion-selective field-effect transistors (Na⁺-ISFET′s). ISFET′s based on these lariat ether amides exhibit excellent Na⁺/K⁺ selectivities (K_Na′K ^Pot = 7 × 10^?3) and Na⁺/H⁺ selectivities (K_Na′H ^Pot = 3 × 10^?3) with good selectivities for Na⁺ over other alkali metal cations and alkaline-earth metal cations. High sensor durability was obtained for these ISFET′s.     

Use of Microspherical Sulfonated Hypercrosslinked Polystyrene in Ion Chromatography

The possibility of applying sulfonated cation exchangers on the basis of hypercrosslinked polystyrene (HCPS) of different ion-exchange capacity for the ion-chromatographic separation of alkali metal and ammonium cations was demonstrated. The effect of the nature and concentration of the eluent, the temperature of the chromatographic column, additions of an organic solvent to the eluent, and the ion-exchange capacity of the sorbent on the retention of cations was examined. An unusual selectivity of the sorbent for lithium and ammonium cations was found; the elution order can change for the Li⁺/Na⁺ and Rb⁺/NH⁺ ₄ pairs depending on the nature of the eluent, the temperature, additions of an organic solvent, and the structural characteristics of the sorbent. When dilute solutions of nitric acid are used as the eluent, the following elution order of cations was obtained: Na⁺ < Li⁺ < K⁺ < NH⁺ ₄ < Rb⁺ < Cs⁺ Mg²⁺ < Sr²⁺ < Ca²⁺ < Ba²⁺. Under the optimum conditions of separation (1 mM solution of sulfuric acid, 20°C) on sulfonated HCPS with an ion-exchange capacity of 0.07 mequiv/g, the separation of ammonium and alkali metal cations was achieved within 17 min.     

Synthesis of novel chromogenic azocalix[4]arenemonoquinones and their binding with alkali metal cations

Five new chromogenic azocalix[4]arenemonoquinones have been synthesized, characterized and examined for their interaction with alkali metal cations (Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺) by UV-visible spectroscopic and cyclic voltammetric techniques. It has been determined that 4a selectively exhibits a significant bathochromic shift in its UV-visible spectrum on interaction with potassium ion in comparison to its treatment with other alkali metal cations. The binding stoichiometry of 4a and potassium ion was established to be 1:1 with an association constant of 3.27 × 10⁴ M^?1. Cyclic voltammetric experiments in 4:1 dichloromethane-acetonitrile also revealed a significant anodic shift (ΔE _(1/1′) = 115 mV) of the original redox waves of 4a on interaction with potassium ion.     

Synthesis and cation binding properties of fluorescent calix[4]arene derivatives bearing tryptophan units at the lower rim

The fluorescent peptidocalixarenes, 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(O-methyl-l-tryptophanylcarbonylmethoxy)calix[4]arene (1) and 5,11,17,23-tetra-tert-butyl-25,27-di(O-methyl)-26,28-bis(O-methyl-l-tryptophanylcarbonylmethoxy)calix[4]arene (2), were prepared by introducing tryptophan subunits at a lower calixarene rim. Coordination abilities of 1 and 2 towards Eu(III) and alkali metal cations were studied by spectrophotometric, spectrofluorimetric, conductometric and potentiometric titrations in acetonitrile at 25°C. Rather strong complexation was observed for smaller alkali metal cations Li⁺ and Na⁺ (log K _Li1 >6, log K _Li2 >6, log K _Na1  = 8.25, log K _Na2  = 6.94), and moderate for K⁺ (log K _K1  = 5.09, log K _K2  = 4.09). Larger Rb⁺ and Cs⁺ cations did not fit in the ion binding site of 1 so no complexation was detected, whereas the more flexible ligand 2 accommodated Rb⁺ cation (log K _Rb2  = 3.44). The fluorescence of 1 (λ_ex = 280 nm, λ_em = 340 nm) was remarkably quenched by Eu(III). Stability constant of 1:1 (Eu³⁺:1) complex determined spectrofluorimetrically amounted to log K _Eu1  = 6.16.     

Complex forming and extraction properties of oligo benzo-fused crown ethers

The complex forming properties with alkali metal and ammonium ions of a series of oligo benzo-condensed 18-crown-6 ethers1–8 having a different gradation of lipophilicity and of molecular rigidity are investigated by voltammetry at the interface of two immiscible electrolyte solutions (ITIES) and by a liquid-liquid extraction technique. The experimental results obtained in the two phase system H₂O/nitrobenzene are discussed in relation to the structure of the crown and the cation type. The stability constants for the 1 : 1 complexes of Na⁺, K⁺, Rb⁺, Cs⁺ and NH ₄ ⁺ in nitrobenzene have been determined and compared with the extraction constants for the 1: 1 complexes of Na⁺ and K⁺ and for the 1 : 1 and 1 : 2 complexes of Cs⁺, showing the effect of oligo benzo condensation for the 18-crown-6 system.     

New 2-methylenepropylene-bridged cryptands with high sodium ion selectivity: A thermodynamic study of complexation

Thermodynamic quantities for the interactions of mono- and tri(2-methylenepropylene)-bridged cryptands, cryptand [3.3.1], cryptand [2.2.2], and 18-crown-6-with Na⁺, K⁺, Rb⁺, and Cs⁺ have been determined by calorimetric titration in an 80:20 (v/v) methanol: water solution at 25°C. Incorporation of the 2-methylenepropylene (–CH₂C(=CH₂)CH₂–) bridge(s) into cryptand [2.2.2] results in a large change in the ligand-cation binding properties. Tri(2-methylenepropylene)-bridged cryptand [2.2.2] (2) shows high selectivity factors for Na⁺ over K⁺ and other alkali cations, while 2-methylenepropylene-bridged cryptand [2.2.2.] (1) selects K⁺ over Na⁺, as does cryptand [2.2.2]. The K⁺/Na⁺ selectivity is reversed with increasing number of 2-methylenepropylene bridges. This observation indicates that increasing the number of 2-methylenepropylene bridges on cryptand [2.2.2] favors complexation of a small cation over a large one. The logK values for the formation of 1 and 2 complexes (except 1-Cs⁺ and 2-Na⁺) decrease as compared with those for the corresponding [2.2.2] complexes. Formation of six-membered chelate ring(s) by the propyleneoxy unit(s) of 1 and 2 with a cation stabilizes the cryptate complexes of the small Na⁺ and destabilizes the complexes of large alkali metal cations. Thermodynamic data indicate that the stabilities of the cryptate complexes studied are dominated mostly by the enthalpy change. In most cases, both stabilization of Na⁺ complexes and destabilization of the complexes of large alkali metal cations by six-membered chelate ring(s) also result from an enthalpic effect. Cryptand [3.3.1] shows a selectivity for K⁺ over Cs⁺, despite its two long CH₂(CH₂OCH₂)₃CH₂ bridges. The [3.1] macroring portion of [3.3.1]may be too small to effectively bind the Cs⁺, resulting in the low stability of the Cs⁺ complex.     

Synthesis and alkali metal complexation studies of novel cage-functionalized cryptands

The synthesis of novel cage-functionalized cryptands 1–5 containing adamantane-, 2-oxaadamantane- or noradamantane-moiety [i.e., 1,3-diethyladamantano[2.2.0]cryptand (1), 1,3-diethoxyadamantano[2.2.2]cryptand (2), 1,3-di[(ethyloxy)methyl]adamantano[2.2.2]-cryptand (3), 1,3-di[(ethyloxy)methyl]-2-oxaadamantano[2.2.3]cryptand (4), and 1,2-diethyloxynoradamantano[2.2.2]cryptand (5)] and their alkali metal binding properties are reported. The results obtained by extraction experiments showed that all the cryptands displayed lower extraction capabilities than the parent [2.2.2]cryptand. However, cryptands 1 and 2 showed much higher selectivity toward K⁺ than the reference [2.2.2]cryptand. When the third bridge is enlarged by two additional CH₂-groups as well as by two oxygen atoms, as in cryptands 3 and 4, the complexational abilities for bigger cations (K⁺, Rb⁺ and Cs⁺) are enhanced. Cryptand 5 displayed very good extraction capabilities of all cations, but showed practically no selectivity towards any of the alkali metal cation. The experimental findings are corroborated by calculation studies consisting of force field based conformational search using Monte Carlo method followed by investigation of the stabilities of the complexes of cryptands with Na⁺ and K⁺ metal ions in chloroform by means of quantum chemical calculations at the density functional theory level.     

Complexing properties of two benzocrown-ether moieties arranged at a cyclobutane ring system

Biscrown ethers 2a-c and 3a-c arranged at a cyclobutane ring were prepared by intermolecular [2+2] photocycloaddition of vinylated benzocrown ethers. The complexing behavior of 2a-c toward alkali metal cations was evaluated by ESI-MS analysis, liquid-liquid extraction, and the comparison of complexing stability constant. An intramolecular sandwich-type 1:1 (host/guest) complexation was observed by ESI-MS analysis in the competitive system where 2a-Na⁺, 2b-K⁺, and 2c-Cs⁺ were formed selectively. In the liquid-liquid extraction, however, 2a hardly extracted any cation, while both 2b and 2c efficiently extracted larger cations such as K⁺, Rb⁺, and Cs⁺. It was found that the complexing stability constant of 2a-Na⁺ is lower than that of benzo-15-crown-5-Na⁺ though extraordinarily high values were obtained for 2b-K⁺ and 2c-Cs⁺ complexes compared with those of 18-crown-6-K⁺ and dibenzo-24-crown-8-Cs⁺ complexes, respectively. Hence, the excellent complexing ability was achieved by using the cyclobutane ring, which strongly preorganized two benzocrown-ether moieties for the larger alkali metal cations.     

一种基于硫杂杯[4]芳烃的高效银离子载体

合成了基于下缘含有酰肼基团的硫杂杯芳烃衍生物的银离子载体1,其核磁研究证实硫杂杯芳烃以1,3-交替构象存在,并且通过非竞争萃取实验和竞争萃取实验研究了它对碱金属和过渡金属离子（Li⁺, Na⁺, K⁺, Cs⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and Ag⁺）的键合能力和选择性。实验结果表明：将酰肼基团引入1,3-交替构象的硫杂杯芳烃骨架的下缘可以提高其对Ag⁺的键合能力和选择性,同时,对Cu²⁺的萃取能力较弱,对碱金属离子和其它的重金属离子几乎没有萃取能力。进一步的核磁滴定和电喷雾质谱实验显示化合物1与银离子形成配合物的配合计量比为1：1,由此推断主要由“N-Ag⁺”配位键以及硫杂杯芳烃骨架的协同作用构成了化合物1与银离子的配合模式。