离子对色谱法同时分离测定吡啶及咪唑离子液体阳离子

建立了用紫外检测的反相离子对色谱梯度淋洗同时分离测定4种吡啶离子液体阳离子和5种咪唑离子液体阳离子的方法。实验采用ZORBAX Eclipse XDB-C18反相色谱柱,以离子对试剂水溶液(用柠檬酸调节pH值)+乙腈为流动相,考察了离子对试剂种类和浓度、乙腈浓度和色谱柱温度对保留的影响,探讨了相关保留规律,确定最佳色谱条件为:流速1.0 mL/min、柱温30℃,以1.0 mmol/L庚烷磺酸钠水溶液(pH 4.0)-乙腈为淋洗液进行梯度洗脱。在此条件下,4种吡啶阳离子和5种咪唑阳离子在15 min内达到基线分离。检出限(S/N=3)为0.31～0.54 mg/L,峰面积的相对标准偏差为0.10%～0.75%。将该方法用于实验室合成的离子液体样品分析,加标回收率为94%～98%。该方法准确、可靠,具有较好的实用性。     

Magnetic phase transitions in transition-metal complexes with triazole derivatives

Three divalent transition-metal (Co, Ni and Cu) complexes with the organic anion, 1,2,4-triazolato (tr), as a ligand molecule were prepared by means of hydrothermal syntheses and their magnetic properties were investigated by SQUID magnetometry. The Co(tr)₂ and Cu(tr)₂ complexes exhibit long range ordering below 8 and 30 K, respectively, while the Ni(tr)₂ complex does not show any magnetic phase transition down to 1.8 K. The magnetization isotherms of Co(tr)₂ and Cu(tr)₂ measured at 2.0 K show hysteresis loops with the coercive fields of 0.5 and 4.7 kOe, respectively. At temperatures higher than about 50 K, the temperature dependence of the magnetic susceptibility of Co(tr)₂, Ni(tr)₂ and Cu(tr)₂ follows the Curie-Weiss law with the Curie constants of 2.95, 0.945 and 0.420 emu K mol⁻¹ and the Weiss temperatures of −62, −74 and −97 K, respectively. These results suggest that the magnetically ordered phases observed in Co(tr)₂ and Cu(tr)₂ at low temperatures come from antiferromagnetic interactions resulting in canted arrangements of magnetic moments of the transition-metal cations. We discuss here the magnetic interactions in these transition-metal complexes by referring the results of the magnetization measurements.     

Fine‐Tuning of Lewis Acidity: The Case of Borenium Hydride Complexes Derived from Bis(phosphinimino)amide Boron Precursors

Reactions of bis(phosphinimino)amines LH and L′H with Me₂S ? BH₂Cl afforded chloroborane complexes LBHCl ( 1 ) and L′BHCl ( 2 ), and the reaction of L′H with BH₃ ? Me₂S gave a dihydridoborane complex L′BH₂ ( 3 ) (LH=[{(2,4,6‐Me₃C₆H₂N)P(Ph₂)}₂N]H and L′H=[{(2,6‐iPr₂C₆H₃N)P(Ph₂)}₂N]H). Furthermore, abstraction of a hydride ion from L′BH₂ ( 3 ) and LBH₂ ( 4 ) mediated by Lewis acid B(C₆F₅)₃ or the weakly coordinating ion pair [Ph₃C][B(C₆F₅)₄] smoothly yielded a series of borenium hydride cations: [L′BH]⁺[HB(C₆F₅)₃]^? ( 5 ), [L′BH]⁺[B(C₆F₅)₄]^? ( 6 ), [LBH]⁺[HB(C₆F₅)₃]^? ( 7 ), and [LBH]⁺[B(C₆F₅)₄]^? ( 8 ). Synthesis of a chloroborenium species [LBCl]⁺[BCl₄]^? ( 9 ) without involvement of a weakly coordinating anion was also demonstrated from a reaction of LBH₂ ( 4 ) with three equivalents of BCl₃. It is clear from this study that the sterically bulky strong donor bis(phosphinimino)amide ligand plays a crucial role in facilitating the synthesis and stabilization of these three‐coordinated cationic species of boron. Therefore, the present synthetic approach is not dependent on the requirement of weakly coordinating anions; even simple BCl₄^? can act as a counteranion with borenium cations. The high Lewis acidity of the boron atom in complex 8 enables the formation of an adduct with 4‐dimethylaminopyridine (DMAP), [LBH ? (DMAP)]⁺[B(C₆F₅)₄]^? ( 10 ). The solid‐state structures of complexes 1 , 5 , and 9 were investigated by means of single‐crystal X‐ray structural analysis.     

The Key Role of U28 in the Aqueous Self‐Assembly of Uranyl Peroxide Nanocages

For 11 years now, the structural diversity and aesthetic beauty of uranyl–peroxide capsules have fascinated researchers from the diverse fields of mineralogy, polyoxometalate chemistry, and nuclear fuel technologies. There is still much to be learned about the mechanisms of the self‐assembly process, and the role of solution parameters including pH, alkali template, temperature, time, and others. Here we have exploited the high solubility of the UO₂²⁺/H₂O₂/LiOH aqueous system to address the effect of the hydroxide concentration. Important techniques of this study are single‐crystal X‐ray diffraction, small‐angle X‐ray scattering, and Raman spectroscopy. Three key phases dominate the solution speciation as a function of time and the LiOH/UO₂²⁺ ratio: the uranyl–triperoxide monomer [UO₂(O₂)₃]^4?and the two capsules [(UO₂)(O₂)(OH)]₂₄^24?(U₂₄) and [(UO₂)(O₂)_1.5]₂₈^28?(U₂₈). When the LiOH/U ratio is around three, U₂₈ forms rapidly and this cluster can be isolated in high yield and purity. This result was most surprising and challenges the hypothesis that alkali templating is the most important determinant in the cluster geometry. Moreover, analogous experiments with KOH, NH₄OH, and TEAOH (TEA=tetraethylammonium) also rapidly yield U₂₈, which suggests that U₂₈ is the kinetically favored species. Complete mapping of the pH–time phase space reveals only a narrow window of the U₂₈ dominance, which is why it was previously overlooked as an important kinetic species in this chemical system, as well as others with different counterions.     

Apparent Molar Volumes of Multicharged Cations in Dimethyl Sulfoxide Solutions at 25°C

Densities for DMSO solutions of iron(III), aluminium(III), beryllium(II) and magnesium(II) perchlorates and silver nitrate are reported. Densities for DMSO solutions of tetraethylammonium perchlorate and nitrate and tetrabutylammonium perchlorate and tetraphenylborate are also presented. The partial molar volumes of the DMSO-solvated cations are derived and discussed in terms of variation with the charge number.     

Influence of electrolyte characteristics on the electrochemical parameters of electrical double layer capacitors

Electrical double layer capacitors based on ideally polarizable nanoporous carbon electrodes in propylene carbonate with the addition of different 1 M Me₃EtNBF₄, Me₂Et₂NBF₄, MeEt₃NBF₄, Et₄NBF₄, Et₃PrNBF₄ and Et₃BuNBF₄ electrolytes have been tested by cyclic voltammetry, chronoamperometry and electrochemical impedance methods. The limits of ideal polarizability, low-frequency limiting capacitance and series resistance, time constant, Ragone plots (energy density vs. power density dependencies) and other characteristics have been discussed. The influence of the electrolyte molar mass on the electrochemical characteristics of the nanoporous carbon electrode cells has been established. The applicability limits of the Srinivasan and Weidner model have been tested.     

Anion dependent molecular recognition of cations

In DMF-d₇ tetrabenzimidazole cavitands 2 exist as monomeric species and vase-like conformers. Several possible arrangements of the four benzimidazole NHs are indicated by ¹H NMR spectroscopy. The cavitands form 1:1 inclusion complexes with tetraethyl ammonium and phosphonium cations only when strong hydrogen bonding anions like chloride or acetate are present. These complexes are stable on the NMR time scale at 295 K feature a C_2V-symmetrical arrangement of benzimidazole functions. The stability of the C_2V-symmetrical tetramethylammonium acetate complex is independent of the temperature. In contrast, tetramethylammonium and phosphonium chloride complexes exist at 233 K as several isomers. This complicated behavior is, in part, attributed to the hydrogen bonding interactions between the anions and the NH groups of benzimidazole functions.     

Absolute potassium cation affinities (PCAs) in the gas phase

The potassium cation affinities (PCAs) of 136 ligands (20 classes) in the gas phase were established by hybrid density functional theory calculations (B3-LYP with the 6-311+G(3df,2p) basis set). For these 136 ligands, 70 experimental values are available for comparison. Except for five specific PCA values-those of phenylalanine, cytosine, guanine, adenine (kinetic-method measurement), and Me(2)SO (by high-pressure mass spectrometric equilibrium measurement)-our theoretical estimates and the experimental affinities are in excellent agreement (mean absolute deviation (MAD) of 4.5 kJ mol(-1)). Comparisons with previously reported theoretical PCAs are also made. The effect of substituents on the modes of binding and the PCAs of unsubstituted parent ligands are discussed. Linear relations between Li+/Na+ and K+ affinities suggest that for the wide range of ligands studied here, the nature of binding between the cations and a given ligand is similar, and this allows the estimation of PCAs from known Li+ and/or Na+ affinities. Furthermore, empirical equations relating the PCAs of ligands with their dipole moments, polarizabilities (or molecular weights), and the number of binding sites were established. Such equations offer a simple method for estimating the PCAs of ligands not included in the present study.