Synthesis of a symmetric cylindrical bis(crown ether) host and its complexation with paraquat

The first cylindrical host for paraquat derivatives was prepared and characterized by X-ray analysis. Its complex with paraquat has 1:2 stoichiometry. The complexation is statistical and strong as shown by proton NMR characterization, electrospray mass spectrometry, and X-ray analysis.     

Guest-dependent complexation of triptycene-based macrotricyclic host with paraquat derivatives and secondary ammonium salts: a chemically controlled complexation process

The triptycene-based macrotricyclic host containing two dibenzo-[24]-crown-8 moieties has been found to form stable 1:1 or 1:2 complexes in different complexation modes with different functional paraquat derivatives and secondary ammonium salts in solution and in the solid state. Consequently, the alkyl-substituted paraquat derivatives thread the lateral crown cavities of the host to form 1:1 complexes. It was interestingly found that the paraquat derivatives containing two beta-hydroxyethyl or gamma-hydroxypropyl groups form 1:2 complexes, in which two guests thread the central cavity of the host. Other paraquat derivatives containing terminal hydroxy, methoxy, 9-anthracylmethyl, and amide groups were included in the cavity of the host to form 1:1 complexes. Moreover, the host also forms a 1:2 complex with two 9-anthracylmethylbenzylammonium salts, in which the 9-anthracyl groups were selectively positioned outside the lateral crown cavities. The competition complexation process between the host and two different guests (the propyl-substituted paraquat derivative and a dibenzylammonium salt) could be chemically controlled.     

Novel triptycene-based cylindrical macrotricyclic host: synthesis and complexation with paraquat derivatives

[reaction: see text] A novel triptycene-based cylindrical macrotricyclic polyether containing two dibenzo[24]crown-8 cavities has been synthesized and proved to be a highly efficient host for the complexation with paraquat derivatives. Consequently, a new kind of very stable pseudorotaxane-type complex was formed in solution and in the solid state.     

Self-assembly of dendritic tris(crown ether) hexagons and their complexation with dibenzylammonium cations

The construction of a new series of dendritic tris(crown ether) hexagons via coordination-driven self-assembly is described. Combining 120° crown ether-containing diplatinum(II) acceptors with 120° dendritic dipyridyl donors in a 1:1 ratio allows for the formation of a new family of dendritic triple crown ether derivatives with a hexagonal cavity in quantitative yields. The number and the position of these pendant groups can be precisely controlled on the hexagonal metallacycle. The structures of all dendritic multiple crown ether hexgaons are confirmed by multinuclear NMR ((1)H and (31)P), ESI-MS and ESI-TOF-MS, and elemental analysis. The complexation of these dendritic trivalent receptors with dibenzylammonium cations was investigated by (1)H NMR titration experiments. The thermodynamic binding constants between the receptors and guests were established by using the nonlinear least-squares fit method based on (1)H NMR titration experiments. It was found that the association constants of each assembly decrease correspondingly upon the increase of the generation of the dendrons from [G0] to [G3], which might be caused by the steric effect of the dendrons on host-guest complexation.     

Synthesis of a novel triptycene-based molecular tweezer and its complexation with paraquat derivatives

[reaction: see text] A novel triptycene-based molecular tweezer has been synthesized, and its complexation with paraquat derivatives in solution and in the solid state has been studied. Due to its electron-rich cavity, the molecular tweezer could form stable complexes with paraquat derivatives with different functional groups. Moreover, it was also found that formation of the complexes was caused by a charge transfer interaction and the complexes dissociated upon two one-electron reduction of the bipyridinium ring.     

Synthesis,complexation, and photochemistry of benzobisthiazole-based bis(crown ether)

Benzobisthiazole-based bis(crown ether) was synthesized and its complexation with alkali and alkaline earth cations was studied. Photochemical transformations of the free ligand and its complexes with alkaline earth cations involve E,Z-photoisomerization and [2+2] photocycloaddition. Dedicated to Academician N. S. Zefirov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2056–2065, September, 2005.     

Taco grande: a dumbbell bis(crown ether)/paraquat [3](taco complex)

The first paraquat-based [3](taco complex) was successfully prepared from a linear bis(crown ether) host and paraquat as shown by proton NMR characterization and X-ray analysis. It has a dumbbell shape in the solid state. The two crown ether binding sites are independent of each other during their complexation in solution.     

Self-assembly of triptycene-based cylindrical macrotricyclic host with dibenzylammonium ions: construction of dendritic [3]pseudorotaxanes

[reaction: see text] It was found that a cylindrical macrotricyclic host containing two dibenzo[24]crown-8 cavities could self-assemble with two dibenzylammonium salts to form a stable 1:2 complex in solution and in the solid state, in which multiple hydrogen-bonding and pi-pi stacking interactions between the host and the guest played an important role. Furthermore, a series of dendritic pseudorotaxanes were constructed and structurally studied.     

Cation complexation behavior of pyrene- and anthracene-appended new crown ether derivatives

Pyrene- and anthracene-appended new crown ether derivatives have been synthesized by Schiff's base reaction, and cation complexation behavior was investigated by fluorescence spectroscopy measurements. Based on photo-induced electron transfer and intramolecular charge transfer mechanism, the host molecules emit stronger fluorescence in the presence of various cations Na(+), K(+), Rb(+), Cs(+) and NH(4)(+) since the complexation between guest cations and crown ether compounds inhibit partial electron transfer from the nitrogen atom to the chromophores and subsequently fluorescence is enhanced. The binding constants were estimated from the plots of the fraction of binding sites filled for crown ether compound as a function of free-ion concentration. Results show that 15-crown-5 derivatives exhibit higher binding ability with sodium cations while 18-crown-6 derivatives had higher affinity for potassium cations, which is consistent with the hole-size relationship of the crown ethers. Ammonium ion complexation caused largest fluorescence enhancement. It is understood that ammonium ion cannot only complex with crown ether, but also interact directly with the lone pair electrons of nitrogen atom in C=N bond so that electron transfer from the nitrogen atom to chromophores is further inhibited.     

Synthesis of bis(bromomethyl) dimethyl crown ethers and complexation properties of their derivatives having electron-donating sidearms

Several bis(bromomethyl) dimethyl 15-crown-5, 18-crown-6, and 21-crown-7 were prepared according to two methods without protecting reactive bromo substituents. Cis and trans isomers of la are separated and the structures are inferred by considering the complexation property of their derivatives having electron-donating sidearms toward sodium and potassium cations.     

Extraction of alkali metal picrates with poly- and bis(crown ether)s

Extraction of alkali metal picrates by new poly- and bis(crown ether)s containing benzo-15-crown-5 and benzo-18-crown-6 moieties was carried out with chloroform as water-immiscible solvent. The poly- and bis(crown ether)s were found to extract the picrates more effectively than the corresponding monocyclic crown ethers. In particular, poly- and bis(benzo-15-crown-5), and bis(benzo-18-crown-6) are remarkably effective extracting reagents for potassium and rubidium, and for caesium, respectively. Extraction equilibrium constants and the complexation constants in the chloroform phase were also evaluated and the contribution of the complexation constants to the extractability is discussed.     

双冠醚配位作用的热力学性质V. 双(苯并-15-冠-5)与稀土(III)硝酸盐在无水乙腈溶液中分子内夹心配位作用

本文用分光光度滴定法测定了双(苯并-15-冠-5)(1)与轻稀土(III)硝酸盐在无水乙腈溶液中, 20.0-35.0℃时分子内夹心配位作用的稳定常数, 进而计算了配位焓和配位熵, 并与母体苯并15-冠-5(2)的实验结果作了比较。化学计量法表明, 所有稀土硝酸盐均与双(苯并-15-冠-5)形成了1 : 1的配合物。从热力学的观点, 讨论了双冠醚分子结构、尺寸效应和空间构型等配位稳定性的影响。研究结果发现, 双冠醚(1)对于Eu^3^+具有较强的配位能力和配位选择性, Nd^3^+次之。配合物的稳定性主要来自于熵的贡献。     

Novel bis (crown ether)-based potassium sensor for biological applications

Based on structure-selectivity studies on bis-benzo-crown ether derivatives, 2,2-bis[3,4-(15-crown-5)-2-nitrophenylcarbamoxymethyl]tetradecane (BME-44) was designed and synthesized. The performance characteristics of this new, highly lipophilic ionophore of the group of bis-nitrobenzo-15-crown-5 derivatives with urethane linkage when used in liquid membrane electrodes are evaluated with special regard to the requirements of biological and clinical applications. Potentiometric steady-state and flow-through dynamic data are presented to prove the sensor capabilities for clinical and physiological potassium determinations.Dedicated to Professor W. Simon on the occasion of his 60th birthday     

Caesium-selective PVC membrane electrodes based on bis(crown ether)s

Caesium-selective PVC membrane electrodes based on bis(crown ether)s containing benzo-18-crown-6 moieties were prepared using two kinds of plasticizers. Selectivity coefficients for various interfering monovalent ions were determined by the mixed solution method, and were found to relfect the complexing property and extractability of the bis-(benzo-18-crown-6)s. The electrochemical selectivity was also compared with that of the corresponding monocyclic analog and valinomycin.     

A supramolecular poly[3]pseudorotaxane by self-assembly of a homoditopic cylindrical bis(crown ether) host and a bisparaquat derivative

A supramolecular poly[3]pseudorotaxane was prepared by self-assembly of a homoditopic cylindrical bis(crown ether) host and a bisparaquat derivative in solution by host-guest complexation.     

A new cryptand: synthesis and complexation with paraquat

[formula: see text] Inspired by folded, nonpseudorotaxane complexes of bis(m-phenylene)-32-crown-10 systems, we synthesized a new bicyclic crown ether containing two 1,3,5-phenylene units linked by three tetra(ethyleneoxy) units. The new cryptand forms a "pseudorotaxane-like" inclusion complex with N,N'-dimethyl-4,4'-bipyridinium bis(hexafluorophosphate) with association constant Ka = 6.1 x 10(4) M-1, 100-fold greater than that of an analogous simple crown ether.     

Solvent extraction of alkaline earth metal picrates with poly- and bis(crown ether)s

Summary Solvent extraction of alkaline earth metal picrates with poly- and bis(crown ether)s containing benzo-15-crown-5- and benzo-18-crown-6 moieties was carried out in a water-chloroform system. The poly- and bis(crown ether)s showed larger extractability for the metal picrates than the corresponding monocyclic crown ethers. Especially, poly- and bis(benzo-15-crown-5), and bis(benzo-18-crown-6) were found to have relatively high extractability and selectivity for Ba²⁺ and Sr²⁺, respectively.

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Lösungsmittelextraktion von Erdalkalipikraten mit Hilfe von Poly- und Bis-Kronenethern

Zusammenfassung Poly- und Bis-Kronenether mit Benzo-15-krone-5- und Benzo-18-krone-6-Einheiten wurden zur Extraktion von Erdalkalipikraten im Wasser-Chloroform-System verwendet. Die genannten Ether zeigten eine bessere Extraktionsfähigkeit für die Pikrate als die entsprechenden monocyclischen Kronenether. Im Falle von Ba²⁺ und Sr²⁺ ergab sich eine besonders gute Extrahierbarkeit und Selektivität mit Poly- und Bis(benzo-15-krone-5)- und Bis(benzo-18-krone-6)-Ethern.

     

Rotaxane‐type hyperbranched polymers from a crown ether host and paraquat guests containing blocking groups

Rotaxane‐type hyperbranched polymers are synthesized for the first time from A₂B type semi‐rotaxane monomers formed in situ via complexation of bis(m‐phenylene)‐32‐crown‐10 dimethanol ( 1 ) and two paraquat ω‐n‐alkylenecarboxylic acid derivatives with tris(p‐t‐butylphenyl)methylphenylalkylene stoppers ( 8 and 9) . Rotaxane and taco complexes exist in solutions of the hyperbranched polyesters in CD₃CN/CDCl₃ as confirmed by NMR spectroscopy, but the taco complexes, which derive from non‐rotaxanated paraquat units, disappear in DMSO‐d₆. NMR spectroscopy indicates the portion of rotaxanes strongly interlocked by the environment (inner rotaxanes) is larger in HP1?9 , which has longer alkylene spacers, perhaps indicating a higher degree of polymerization. The molecular size increases upon formation of the hyperbranched polymers are confirmed by dynamic light scattering and by viscometry. As with covalent hyperbranched polymers a number of potential applications exist; the unique mechanically linked character and the presence of uncomplexed host and guest moieties foreshadow the use of such systems for their responses to external stimuli with the added benefit of providing molecular recognition sites useful as delivery vehicles. Use of other host‐guest motifs to form the semirotaxane A₂B monomers is possible and complementary systems with higher binding constants will enable efficient syntheses of high molecular weight, mechanically linked hyperbranched polymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1647–1658     

Influence of the angle between two crown ether moieties on supramolecular copolymerization of bis(crown ether)s and bisparaquat homoditopic monomers

Bis(crown ether) homoditopic monomers containing two bis(p-phenylene)-34-crown-10 moieties with different angles(180° for monomer 3,120°for monomer 4,and 60°for monomer 5) and a complementary bisparaquat homoditopic monomer(7) were designed and synthesized.The three bis(crown ether) monomers could organize into linear supramolecular polymers in concentrated solutions in CHCl3/CH3CN with the bisparaquat monomer 7,as demonstrated by 1 H NMR and viscosity studies. The pseudorotaxanes or supramolecular polymers...