两种偶氮苯冠醚的合成及其光致变色机理

报道了4-氮杂15-冠-5-4'-甲氧基偶氮苯和4-氮杂15-冠-5-4'-硝基偶氮苯的合成及其分子内扭曲电荷转移的光致变色机理.     

Solvent Extraction of Sodium with Crown Ethers

Abstract

The solvent extraction separation of sodium was effected with 15-crown-5 (0.01 M) in methylene chloride in presence of 0.01 M picric acid as a counter ion. It was quantitatively extracted at pH 5.0 and was stripped with 3 M hydrochloric acid and determined by flame emission spectroscopy at 589 nm. Sodium was separated from alkali and alkaline earth metals and common anions. The method was extended to the analysis of sodium from real samples.     

两各氮苯冠醚的合成及其及其光致变色机理

报道了４－氮杂１５－－５－４＇－甲氮基偶氮苯和４－氮杂１５－冠－５－４＇－硝基偶氮苯的合成及其分子内扭曲电荷转移的光致变色机理。     

Short and Efficient Synthesis of Thiol Group Functionalized Crown Ethers

A synthesis of thiol group functionalized crown ethers is reported. The reaction is accomplished by the direct chlorosulfonation of simple crown ethers with chlorosulfonic acid and the reduction of the sulfonyl chloride moiety with LiAlH₄ in two steps. This new process is simple to operate, and it generates high‐purity mercaptobenzocrowns with excellent yields.     

Complexes of Mercury(II) Cyanide with Crown Ethers in Dimethylsulfoxide

The complexation of mercury(II) cyanide with macrocyclic ligands 15-crown-5,18-crown-6 and dibenzo-24-crown-8 in dimethylsulfoxide was studied using¹⁹⁹Hg NMR measurements. No significant complexation with 15-crown-5was observed. The stability constants K_s for 1 : 1 complexes with two other ligands were determined and found to be similar, in contrary to the results reported in nitrobenzene. Solvent effects on K_s values obtained are discussed in comparison with the literature data. X-ray crystal structure of Hg(CN)₂.A18-crown-6 was also determined.     

The Complexation of Amino Acids by Crown Ethers and Cryptands in Methanol

Complex formation between several crown ethers and the cryptand (222) and -amino acids in methanol was studied by calorimetric titration. The ligand structure and the donor atoms of the ligands play an important role in determining the measured values of the reaction enthalpies and entropies. However, with the exception of the diaza crown ether (22) all stability constants are of the same order of magnitude. The enthalpic and entropic contributions to the stabilities of the complexes formed compensate each other. In methanolic solution the amino acids exist in their zwitterionic form. This equilibrium can be influenced. Under acidic, neutral or basic conditions different values of the reaction enthalpies are measured for the complexation of some amino acids with 18-crown-6. These results demonstrate that the concentration of the zwitterionic form of the -amino acids can be influenced. Thus the reaction between macrocyclic and macrobicyclic ligands and amino acids should be described by at least two different reaction schemes.     

Extraction of Strontium and Cesium by Dicarbollides, Crown Ethers and Functionalized Calixarenes

The two main classes of extractantsused for the extraction of cesium and strontium aredicarbollides and crown ethers. Dicarbollides wereused on a large scale for the extraction of these twoelements from high-activity waste. The basicdicarbollides present drawbacks since they need to bediluted in polar solvent such as nitrobenzene and theirefficiency strongly decreases as the acidity of liquidwaste increases. Crown ethers enable cesium andstrontium to be extracted if the concentration ofsodium or the acidity of solutions are not too high.Recently, calixarenes blocked in the 1,3-alternateconformation were used for the selective extractionof cesium, even from high-salt waste matrices.     

Unusual Regioselectivity in the Reactions of Chlorocyclophosphazene-Containing Crown Ethers with Dinucleophiles

Abstract

New macrocyclic ligands with cyclophosphazene sub-units, representing geminally diamino-bridged derivatives of BINO-crown type (III), and bisansa-cyclosubstituted ones of chiral PNP cryptand type (IV) have been obtained by the regioselective substitution reactions of monoansa(oxytetraethylenoxy) reactive PNP-crown, N₃P3CI₄[O(CH₂CH20)₄] (II) with the dinucleophiles, like alkylenediamines or sodium diarylates. The supramolecular control of these processes is discussed.     

Nitration of Benzo Crown Ethers with Potassium Nitrate in Polyphosphoric Acid

A general method for the nitration of benzo crown ethers with potassium nitrate in polyphosphoric acid has been developed. Mono- and dinitro derivatives of benzo-12-crown-4, benzo-15-crown-5, dibenzo-18-crown-6, and dibenzo-24-crown-8 have been prepared. The role of complex formation in the regioselective tendency for the nitration of dibenzo-18-crown-6 has been demonstrated.     

Correlation of the Structure and Properties of Alkalides and Electrides That Contain Cryptands or Crown Ethers

Abstract

The structures of several salts that contain alkali metal anions (alkalides) and two that contain trapped electrons (electrides) are correlated with their optical and NMR spectra, and magnetic susceptibilities. The nature of the channels and trapping sites in the two electrides are described.     

磺化冠醚的分子键合与组装

冠醚作为第一代大环主体分子,具有柔性的空腔,因其对金属离子、有机阳离子的络合作用而被广泛用于构筑超分子组装体。磺化冠醚是一种水溶性良好的阴离子型冠醚衍生物,相比于冠醚,它具有更多的键合位点,对金属离子、有机阳离子具有更强的键合和良好的选择性。本文从磺化冠醚的合成,对碱金属离子、镧系金属的络合,对有机阳离子客体的组装等方面介绍了磺化冠醚的研究进展。然后从热力学、晶体结构学的角度综合分析了磺化冠醚键合与组装的模式及驱动力。最后讨论了磺化冠醚的分子键合与组装发展所面临的挑战,并对其应用前景进行了展望。     

新型套索冠醚-金属离子络合性能的紫外光谱法与质谱法研究

本文合成了3种套索冠醚4、5和6,分别测定了它们与Hg^2^ 、Pb^2^ 、Zn^2^ 、cd^2^ 、Ni^2^ 、Co^2^ 、Cu^2^ 、Ag^ 、Tb^3^ 和Eu^3^ 所形成的络合物的紫外吸收光谱,用电喷雾液相色谱-质谱联用仪分别表征了它们与TB^3^ 形成的络合物,结果显示它们对上述金属离子有很好的络合性。     

酰胺型开链冠醚稀土配合物的超声化学合成

用声化学方法合成了八种新的酰胺型开链冠醚稀土配合物,经元素分析,IR,NMR,ES－MS表征,确定了配合物的组成,研究了它们的荧光性质。     

A Convenient and Efficient Method for the Preparation of Unique Fluorophores of Lariat Naphtho‐Aza‐Crown Ethers

New naphtho‐aza‐crown ethers containing different phenolic side‐arms attached through the ortho‐position of the phenol have been prepared under solvent‐free conditions. The starting macrocyclic naphtho‐aza‐crown ether 2 was obtained by treatment of naphthalene dicarboxylic acid diester 1 with diethylenetriamine in EtOH at room temperature for two days without stirring in 77% yield (Scheme 1). Phenolic ligands ( 3 – 14 ) were synthesized by the Mannich reaction of the secondary macrocyclic amine 2 with the substituted phenols using nontoxic and inexpensive CaCl₂. This procedure was applied successfully for the synthesis of Mannich bases from simple secondary amines. The CaCl₂ powder can be reused up to three times after simple washing with dry acetone.     

冠醚增敏稀土配合物荧光增强效应的研究及其应用

本文详细研究了二苯并－１８冠－６对Ｓｍ－ＴＴＡ荧光体系的增敏作用和稀土离子Ｄｙ＾３＋对Ｓｍ－ＴＴＡ－冠醚体系的荧光增强效应，在冠醚存在下，Ｓｍ－ＴＴＡ二元配合物荧光体系的荧光强度增加了２８０倍，Ｓｍ－ＴＴＡ－二苯并－１８－冠－６体系中引入适量的Ｄｙ＾３＋后，使体系的荧光强度提高２６倍，对Ｓｍ－ＴＴＡ－冠醚和Ｓｍ－Ｄｙ－ＴＴＡ－冠醚体系，Ｓｍ的浓度分别在２．０×１０＾－７～１．０×１０＾－５ｍｏｌ／     

DFT Study for a Series of Less-Symmetrical Crown Ethers and Their Complexes with Alkali Metal Cations

A series of ring‐contracted (14‐crown‐5, 17‐crown‐6) and ring‐enlarged (16‐crown‐5, 17‐crown‐5, 19‐crown‐6, 20‐crown‐6) crown ethers and their complexes with alkali‐metal cations Na⁺ and K⁺ had been explored using density functional theory (DFT) at B3LYP/6‐31G* level in order to reveal the effects of the methylene‐chain length in a crown ether. The nucleophilicity of all crown ethers had been investigated by the Fukui functions. The quantum chemistry parameters, such as the energy gap (ΔE), the highest occupied molecular orbital energy (E_HOMO) and the lowest unoccupied molecular orbital energy (E_LUMO) for less‐symmetrical crown ethers and symmetrical frameworks (15‐crown‐5, 18‐crown‐6) had been calculated. In addition, the thermodynamic energies of complexation reactions had also been studied. The results of the DFT calculations show that the methylene‐chain length plays an important role in determining the structure characters of the crown ethers and also strongly influences the properties of the ethers. Some of the calculated results are in a good agreement with the experimental values.     

Apparent Molar Volumes and Adiabatic Compressibilities of Crown Ethers and Glymes in Aqueous Solutions at Various Temperatures

Apparent molar volumes and adiabatic compressibilities of 18-crown-6,15-crown-5, 12-crown-4, tetraglyme, and triglyme were measured at 15, 25, and40°C. Apparent molar expansibilities andK ^o Tvalues were also determined.The contribution of the -CH₂CH₂O- group to the limiting partial molar volumesand compressibilities of cyclic and open-chain ethers are compared. It isconcluded, on the basis of the compressibility results, that there is a subtle differencebetween the hydration of the ethene-oxide group in cyclic and open-chain ethers.     

The Interpretation of Thermodynamic Data for the Complex Formation of Cations with Crown Ethers and Cryptands. Part I: The Reaction Entropy

The complex formation between cationsand crown ethers or cryptands is influenced byenthalpic and entropic contributions. The solvation ofcations and ligands plays an important role andinfluences both thermodynamic parameters. Changes insolvation and their influence upon the reactionentropy is discussed in detail for some selectedreactions in different solvents. Other contributionse.g., from the deformation of the ligands areeliminated. Thus, the results obtained are valid forall complexation reactions between cations andmacrocyclic and macrobicyclic ligands.     

NMR Studies of Mixed-Ligand Lanthanide (III) Complexes. Peculiarities of Molecular Structure, Dynamics and Paramagnetic Properties for Cerium Subgroup Chelates with Crown Ethers

The molecular structure, dynamics and paramagnetic properties of the complex cations [Ln(ptfa)₂ (18-crown-6)]⁺ in deuterated toluene were studied for Ln = La, Ce, Pr and Nd. The activation enthalpy values of 68 ± 5, 55 ± 15 and 60 ± 13 kJ mol^-1 for the 18-crown-6 conformationalinversion processes for the complexcations of Ce, Pr and Nd, respectively,were obtained. Quantitativeinvestigation of the lanthanide-induced chemical shifts shows a monotonic change of a spatial structure and magnetic susceptibility in comparison with the Bleaney predicted dependence. The free energy of molecular inversion activation for 18-crown-6 molecules in the complex cation [Ln(fod)₂(18-crown-6)]⁺ is 74 ± 9 kJ mol^-1 at 363 K, which is a little more than the value of the free energy of activation 64 ± 9 kJ mol^-1 at 363 K in the complex cation [Ln(ptfa)₂(18-crown-6)]⁺.