Recent Progress in the Synthesis of the Monocarba-closo-dodecaborate(−) Anions

This Concept article focuses on the rapid growth in studies of the chemistry of the monocarba-closo-dodecaborate(−) anion (C1 carborane anion). As one of the most stable anions known, the C1 carborane anion has been useful for exploring the chemistry of highly reactive cations. On the other hand, development of novel functional molecules utilizing the unique properties of C1 carborane anion (e.g., σ-aromaticity, rigid spherical skeleton) has progressed more slowly. The main reason for this is the relatively undeveloped state of synthetic chemistry in this area. Recent advances in the synthetic chemistry of C1 carborane anion are highlighted in this Concept article, focusing on cross-coupling reactions at the carbon vertex, direct conversion of B−H bonds, and the synthesis of multivalent weakly coordinating anions. These progressions move this species beyond its well-established role of highly stable “counter” monocharged anion.     

Gravimetric and spectrophotometric determination of hexafluoroantimonate with tetraphenylarsonium chloride, nitron and ferroin

Two methods are described for the gravimetric determination of the hexafluoroantimonate anion with tetraphenylarsonium chloride and nitron as precipitants. In addition, a spectrophotometric method for this anion with ferroin as reagent is described. Hydrolysis of the anion is avoided by using stock solutions of KSbF(6) in N,N-dimethylformanude and adding these directly to concentrated aqueous solutions of the analytical reagent. Interference studies are included on a number of anions.     

牛磺酸和甘氨酸在D290树脂上的离子交换平衡

研究了牛磺酸与甘氨酸在阴离子树脂D290上的离子交换平衡.采用静态法分别进行牛磺酸/氢氧根/D290树脂和甘氨酸/氢氧根/D290树脂体系的离子交换平衡实验并测定等温线;在不同的离子强度下进行了牛磺酸/甘氨酸/氢氧根/D290阴离子交换树脂体系的离子交换平衡实验,测定牛磺酸和甘氨酸在碱性条件下的竞争交换平衡等温线.实验结果表明,牛磺酸在D290阴离子交换树脂上的交换量大于甘氨酸的交换量,阴离子交换树脂对牛磺酸和甘氨酸的选择性系数分别为STau-,OH-=2.55,SGly-,OH-=1.65.在牛磺酸/甘氨酸/氢氧根/D290树脂体系中,D290树脂对牛磺酸/甘氨酸/氢氧根3种离子的选择性从高到底顺序是:牛磺酸＞甘氨酸＞氢氧根.树脂对牛磺酸的选择性要大于对甘氨酸的选择性.随着溶液中离子强度的增大,树脂对牛磺酸与甘氨酸之间的选择性下降.     

Competitive anion transport in desalting of mixtures of organic acids by batch electrodialysis

Desalting and separation of binary and quaternary acid mixtures via batch electrodialysis are investigated in this article. A monoselective cation exchange membrane and either a non-selective or a monoselective anion exchange membrane are employed in the electrodialysis stack. The effects of current density and composition of the initial feed of the electrodialysis stack (employing a non-selective anion exchange membrane) on its performance are studied in experiments involving mixtures of acetic and succinic acids. The effect of the type of the anion exchange membrane on the process performance is examined in desalting experiments involving a mixture of acetic, formic, lactic, and succinic acids. The trends observed in the experiments are interpreted in terms of species-specific parameters (such as molar concentration, charge on ionic species, molecular weight, degree of ionization, and ionic equivalent conductivity) and characteristics of anion exchange membrane used.     

Recognition of Anions by Synthetic Receptors in Aqueous Solution

Natural anion binding systems achieve high substrate affinity and selectivity most often by arranging converging binding sites inside a cavity or cleft that is well shielded from surrounding solvent molecules by the folded peptide chain. Types of interactions employed for anion recognition are electrostatic interactions, hydrogen-bonding, and coordination to a Lewis-acidic metal center. In this review, successful strategies aimed at the development of synthetic receptors active in water or aqueous solvent mixtures are described. It is shown that considerable progress has been made during recent years in the development of potent anion receptors and that for every type of interaction used in nature for anion binding, corresponding synthetic models exist today. Representative examples of these systems are presented with a special emphasis on synthetic receptors whose characterization involved a detailed thermodynamic analysis of complex formation to demonstrate the important interplay between enthalpy and entropy for anion recognition in water.     

Anion-templated assembly of interpenetrated and interlocked structures

The rational development of a general anion templation strategy for the construction of a variety of interpenetrated and interlocked molecular structures based upon the coupling of anion recognition with ion-pairing is described. The success of this anion templation methodology is demonstrated with the halide anion directed assembly of a series of novel [2]pseudorotaxanes containing pyridinium, pyridinium nicotinamide, imidazolium, benzimidazolium and guanidinium threading components and anion binding macrocyclic ligands. Interlocked [2]rotaxane and [2]catenane molecular structures are also synthesised using this anion templation protocol. These interlocked structures feature unique topologically defined hydrogen bond donating binding domains that exhibit a high degree of selectivity for chloride, the templating anion. A series of rhenium(I) bipyridyl containing [2]pseudorotaxane assemblies and a [2]rotaxane further highlight the potential this strategic anion templation approach has in future chemical sensor design and fabrication.     

Dipyrrolyl-functionalized bipyridine-based anion receptors for emission-based selective detection of dihydrogen phosphate

New cationic anion receptors, based on the use of pyrrole-substituted bipyridine and coordinated to transition metals, are described. Specifically, polypyridine-ruthenium and -rhodium cores have been functionalized to generate an anion binding site. The design was chosen to probe the influence of the pyrrole-to-pyrrole separation on anion-binding affinities and selectivities; this distance is greater in the new systems of this report (receptors 1 and 2) relative to that present in related dipyrrolyl quinoxaline based receptors 3 and 4. Solution-phase anion-binding studies, carried out by means of (1)H NMR spectroscopic titrations in [D(6)]DMSO and isothermal titration calorimetry (ITC) in DMSO, reveal that 1 and 2 bind most simple anions with substantially higher affinity than either 3 or 4. In the case of chloride anion, structural studies, carried out by means of single-crystal X-ray diffraction analyses, are consistent with the solution-phase results and reveal that receptors 1 and 2 are both able to stabilize complexes with this halide anion in the solid state.     

弱碱性和强碱性阴离子交换树脂的离子交换平衡的比较SO2-4-Cl——NO-3体系

本文详细地比较了在弱碱性和强碱性阴离子交换树脂上, SO_4~(2-)-Cl~-、NO_3~--Cl~-及NO_3~--SO_4~(2-)二元交换的等温线和修正选择系数。实验测定及理论计算了上述三种二元交换反应的标准自由能的改变量。测得了在弱碱性树脂上的SO_4~(2-)-Cl~--NO_3~-三元交换的等温线。适用于强酸性和强碱性树脂的从二元交换平衡数据推算三元交换平衡数据的方法推广应用于弱碱性树脂。     

Ortho-substituted catechol derivatives: the effect of intramolecular hydrogen-bonding pathways on chloride anion recognition

This paper reports a series of chloride anion receptors containing two catechol head groups connected through their ortho-positions via a spacer chain. The linking group chosen to attach the spacer chain to the catechol units has a major impact on the anion-binding potential of the receptor. Linking groups that are capable of forming stable six-membered intramolecular hydrogen-bonded rings with the catechol O-H groups significantly inhibit the ability of the catechol units to hydrogen bond to chloride anions. However, where the linking groups are only capable of forming five- or seven-membered intramolecular hydrogen-bonded rings, then anion binding via hydrogen bonding through the catechol O-H groups becomes a possibility. This process is solvent dependent; the presence of competitive solvent (e.g., DMSO-d6) disrupts the intramolecular hydrogen-bonding pattern and enhances anion binding relative to simple unfunctionalized catechol. The most effective receptor is that in which the hydrogen-bonding linker (-CH2CONH-) is most distant from the catechol units and can only form a seven-membered intramolecular hydrogen-bonded ring. In this case, the receptor, which contains two catechol units, is a more effective chloride anion binder than simple unfunctionalized catechol, demonstrating that the two head groups, in combination with the N-H groups in the linker, act cooperatively and enhance the degree of anion binding. In summary, this paper provides insight into the hydrogen-bonding patterns in ortho-functionalized catechols and the impact these have on the potential of the catechol O-H groups to hydrogen bond to a chloride anion.     

Anion binding versus intramolecular hydrogen bonding in neutral macrocyclic amides

Although amide groups are important hydrogen-bond donors in natural and synthetic anion receptors, studies on structure-affinity relationships of amide-based macrocyclic receptors are still very limited. Therefore, we synthesized a series of macrocyclic tetraamides 5-8 derived from 1,3-benzenedicarboxylic (isophthalic) acid and aliphatic alpha,omega-diamines of different lengths. (1)H NMR titrations in DMSO solution show that the anion affinity of these receptors decreases with increasing size of the macrocycle irrespective of the anion, and this suggests a minor role of geometric complementarity. Comparison with their previously studied pyridine congeners reveals that the isophthalic acid based macrocycles are less potent, in contrast to what was found for simple model diamides. Combined theoretical and experimental structural studies were carried out to determine the reasons behind this behaviour. The results show that the unexpectedly low anion binding ability of the isophthalic acid-based receptors is due to the self-complementary nature of the isophthalic bis-amide fragments: when two such moieties are present within a sufficiently flexible macrocycle, they adopt syn-anti conformations and bind each other by two strong intramolecular hydrogen bonds that close the macrocyclic cavity. Nevertheless, anion binding is able to break these hydrogen bonds and switch a macrocycle into a convergent all-syn conformation. Despite the ill-preorganized conformation, 20-membered receptor 6 is better than either its open-chain analogue (macrocyclic effect) and/or its isomer having differently placed carbonyl groups. The crystal structures of four anion complexes of the macrocyclic receptors are reported. X-ray studies and solution NMR data confirmed the inclusive nature of the complexes and pointed to strong involvement of aromatic CH hydrogen atoms in anion binding.     

Recognition of Anions by Synthetic Receptors in Aqueous Solution

Natural anion binding systems achieve high substrate affinity and selectivity most often by arranging converging binding sites inside a cavity or cleft that is well shielded from surrounding solvent molecules by the folded peptide chain. Types of interactions employed for anion recognition are electrostatic interactions, hydrogen-bonding, and coordination to a Lewis-acidic metal center. In this review, successful strategies aimed at the development of synthetic receptors active in water or aqueous solvent mixtures are described. It is shown that considerable progress has been made during recent years in the development of potent anion receptors and that for every type of interaction used in nature for anion binding, corresponding synthetic models exist today. Representative examples of these systems are presented with a special emphasis on synthetic receptors whose characterization involved a detailed thermodynamic analysis of complex formation to demonstrate the important interplay between enthalpy and entropy for anion recognition in water.This revised version was published online in July 2005 with a corrected issue number.     

Anion Exchange-Adsorption on Low Capacity Anion Exchangers: Separation of Organic Acids,Amino Acids,Small Chain Peptides

Abstract

The variables that influence the retention of organic analyte anions on a macroporous, high surface area polystyrenedivinyl-benzene copolymer that is chemically modified by attaching tetraalkylammonium groups to the copolymer surface are identified and studied as a function of anion exchange capacity. A combined adsorption-anion exchange retention of the organic analyte anion is possible providing the analyte has both a hydrophophic center and an anionic charge site. As the column anion exchange capacity (0 to 173 μeq of anion exchange sites/column was studied) increases, analyte retention due to adsorption decreases and retention due to anion exchange increases. The factors influencing organic analyte anion retention by adsorption are low anion exchange capacity and mobile phase solvent composition, type of organic modifier, and pH for analytes that are weak organic acids. For anion exchange the major factors are a high anion exchange     

Anthralin: primary products of its redox reactions

One-electron reduction significantly enhances the ability of anthralin, 1, to act as a hydrogen atom donor. On annealing of an MTHF glass in which the radical anion of anthralin, 1*-, is generated radiolytically, this species decays mainly by loss of H* to give the anthralyl anion, 2- . On the other hand, radicals formed on radiolysis of matrices that are suitable for the generation of radical anions or cations are capable to abstract H* from anthralin to give the anthralyl radical, 2* . Both 2- and 2* are obtained simultaneously by mesolytic cleavage of the radical anion of the anthralin dimer. Contrary to general assumptions, the anthralyl radical is found to be much more reactive toward oxygen than the anion. All intermediates are characterized spectroscopically and by reference to quantum chemical calculations. Attempts to generate the radical cation of anthralin by X-irradiation of an Ar matrix containing anthralin led also to significant formation of its radical anion, i.e., anthralin acts apparently as an efficient electron trap in such experiments.     

Unexpectedly strong anion–π interactions on the graphene flakes

Interactions of anions with simple aromatic compounds have received growing attention due to their relevancy in various fields. Yet, the anion–π interactions are generally very weak, for example, there is no favorable anion–π interaction for the halide anion F^? on the simplest benzene surface unless the H‐atoms are substituted by the highly negatively charged F. In this article, we report a type of particularly strong anion–π interactions by investigating the adsorptions of three halide anions, that is, F^?, Cl^?, and Br^?, on the hydrogenated‐graphene flake using the density functional theory. The anion–π interactions on the graphene flake are shown to be unexpectedly strong compared to those on simple aromatic compounds, for example, the F^?‐adsorption energy is as large as 17.5 kcal/mol on a graphene flake (C₈₄H₂₄) and 23.5 kcal/mol in the periodic boundary condition model calculations on a graphene flake C₁₁₃ (the supercell containing a F^? ion and 113 carbon atoms). The unexpectedly large adsorption energies of the halide anions on the graphene flake are ascribed to the effective donor–acceptor interactions between the halide anions and the graphene flake. These findings on the presence of very strong anion–π interactions between halide ions and the graphene flake, which are disclosed for the first time, are hoped to strengthen scientific understanding of the chemical and physical characteristics of the graphene in an electrolyte solution. These favorable interactions of anions with electron‐deficient graphene flakes may be applicable to the design of a new family of neutral anion receptors and detectors. © 2012 Wiley Periodicals, Inc.     

An Ionophore‐Based Anion‐Selective Optode Printed on Cellulose Paper

A general anion‐sensing platform is reported based on a portable and cost‐effective ion‐selective optode and a smartphone detector equipped with a color analysis app. In contrast to traditional anion‐selective optodes using a hydrophobic polymer and/or plasticizer to dissolve hydrophobic sensing elements, the new optode relies on hydrophilic cellulose paper. The anion ionophore and a lipophilic pH indicator are inkjet‐printed and adsorbed on paper and form a “dry” hydrophobic sensing layer. Porous cellulose sheets also allow the sensing site to be modified with dried buffer that prevents any sample pH dependence of the observed color change. A highly selective fluoride optode using an Al^III‐porphyrin ionophore is examined as an initial example of this new anion sensing platform for measurements of fluoride levels in drinking water samples. Apart from Lewis acid–base recognition, hydrogen bonding recognition is also compatible with this sensing platform.     

Anion–π Catalysis of Enolate Chemistry: Rigidified Leonard Turns as a General Motif to Run Reactions on Aromatic Surfaces

To integrate anion–π, cation–π, and ion pair–π interactions in catalysis, the fundamental challenge is to run reactions reliably on aromatic surfaces. Addressing a specific question concerning enolate addition to nitroolefins, this study elaborates on Leonard turns to tackle this problem in a general manner. Increasingly refined turns are constructed to position malonate half thioesters as close as possible on π‐acidic surfaces. The resulting preorganization of reactive intermediates is shown to support the disfavored addition to enolate acceptors to an absolutely unexpected extent. This decisive impact on anion–π catalysis increases with the rigidity of the turns. The new, rigidified Leonard turns are most effective with weak anion–π interactions, whereas stronger interactions do not require such ideal substrate positioning to operate well. The stunning simplicity of the motif and its surprisingly strong relevance for function should render the introduced approach generally useful.     

Anion radicals of di-trans-[12]annulene and heptalene in a one-pot synthesis from a common fire retardant

[reaction: see text] Low temperature (-100 degrees C) dehydrohalogenation of 1,2,5,6,9,10-hexabromocyclododecane (a common fire retardant) with potassium tert-butoxide in THF followed by one-electron reduction yields the anion radical of the di-trans form of [12]annulene. This system yields a well-resolved EPR signal that reveals that most of the spin density resides on one side (the planar side) of the anion radical. Five of the carbons in this [12]annulene system are twisted from the plane of the remaining seven carbons, and the rate of rearrangement between the degenerate conformations is on the EPR time scale (k = 10(6)-10(7) s(-1)). Warming of the solution results in the formation of a sigma-bond between the two internal carbons, loss of molecular hydrogen, and consequent generation of the anion radical of heptalene. Tractable quantities of neutral heptalene can be obtained via the reoxidation of this anion radical with iodine.     

Anion recognition by neutral macrocyclic amides

Although amides often serve as anchoring groups in natural and synthetic anion receptors, the structure-affinity relationship studies of amide-based macrocyclic receptors are still very limited. Therefore, we decided to investigate the influence of the size of the macroring on the strength and selectivity of anion binding by uncharged, amide-based receptors. With this aim, we synthesized a series of macrocyclic tetraamides derived from 2,6-pyridinedicarboxylic acid and aliphatic alpha,omega-diamines of different lengths. X-ray analysis shows that all ligands studied adopt expanded conformations in the solid state with the convergent arrangement of all four hydrogen-bond donors. 1H NMR titrations in DMSO solution revealed a significant effect of the ring size on the stability constants of anion complexes; the 20-membered macrocyclic tetraamide 2 is a better anion receptor than its both 18- and 24-membered analogues. This effect cannot be interpreted exclusively in terms of matching between anion diameter and the size of macrocyclic cavity, because 2 forms the most stable complexes with all anions studied, irrespective of their sizes. However, geometric complementarity manifests in extraordinarily high affinity of 2 towards the chloride anion. The results obtained for solutions were interpreted in the light of solid-state structural studies. Taken together, these data suggest that anion binding by this family of macrocycles is governed by competitive interplay between their ability to adjust to a guest, requiring longer aliphatic spacers, and preorganization, calling for shorter spacers. The 20-membered receptor 2 is a good compromise between these factors and, therefore, it was selected as a promising leading structure for further development of anion receptors. Furthermore, the study of an open chain analogue of 2 revealed a substantial macrocyclic effect. X-ray structure of the acyclic model 14 suggests that this may be due to its ill-preorganized conformation, stabilized by two intramolecular hydrogen bonds.     

利用荧光屏探测器质谱方法研究邻位二氯苯的电子贴附解离

我们在自制的负离子速度成像装置上发展了负离子质谱技术。测量获得了电子贴附解离邻位二氯苯产物Cl^-;的0.2至8 eV效率谱,并且在两个峰位1.2和6.0 eV 测量了其切片速度影像。     

Acidity of carboxylic acids: a rebuttal and redefinition

A recent theory of ionization of carboxylic acids divided the process of ionization into two steps and attributed the main importance to the electrostatic potential of the acid molecule. The origin of the acidity was thus seen in the high energy of the acid molecule and not in the stabilization of the anion by resonance. In this paper, the theory was revised on the basis of further calculations at an MP2/6-31++G(2d,p) level which followed in two steps the reverse process, protonation of the formate anion. The results were compared to those of the methanolate anion as reference. A contradictory conclusion was obtained: the reason for the acidity is in the electrostatic potential of the anion. As a model compound without resonance, 2,2,2-trifluoroethanol was investigated in the same way. The results were qualitatively similar, although any resonance in the anion is not possible. One can conclude that the acidity of carboxylic acids is due to the low energy of their anions; this follows unambiguously from the isodesmic reactions on the basis of either the experimental enthalpies of formation or the calculated energies. It is more difficult to decide whether this low energy is caused by resonance, because any model of the carboxylate anion without resonance is necessarily imperfect and the whole concept is not exactly defined. Several such models were reexamined and improved by separating the effect operative in the anion from those in the neutral acid molecule. While the electrostatic model did not allow any significant conclusion, two models based on VB calculation and on correlation analysis, respectively, furnished qualitatively concordant results: resonance in the anion is diminished by the resonance in the acid molecule, and both together are responsible for less than one-half of the acidity enhancement as compared to the acidity of alcohols. The ratio is reversed in water solution: resonance is then the more important factor responsible for some two-thirds of the enhanced acidity.