Double Molecular Encapsulation of Tetrahydrofuran by an Amphiphilic Calix-[4]-arene

The crystal structure of para-octanoylcalix-[4]-arene·2 tetrahydrofuran complex reveals double inclusion of the guest molecules, one deep in the aromatic cavity and the other held in a four-fingered molecular hand formed by the aliphatic chains, the inclusion changes the molecular packing from a bilayer system in the absence of guest, to a head-to-tail antiparallel chain packing.This revised version was published online in July 2005 with a corrected issue number.     

Synthesis and NMR conformational studies of p-tert-butyldihomooxacalix[4]-arene derivatives

Abstract

The tetramethyl (2) and tetraethyl (3) ethers, and the tetraacetate (4) derivatives of the p-tert-butyldihomooxacalix[4]arene were prepared. The mobility of these compounds studied by temperature-dependent ¹H NMR spectroscopy. For the tetraacetate derivative, at room temperature, 1,2- or 1,3-alternate conformations are suggested. Those conformations were confirmed by NOE difference and COSY spectra for the tetraethyl ether derivative in CDCl₃ at -20°C.     

The Use of Electrospray Mass Spectrometry (ES/MS) for the Differential Detection of Some Steroids as Calix-[n]-arene Sulphonate Complexes

Non-covalent inclusion complexes formed between three p-sulphonato-calix-[n]-arenes (1 n = 4, 2 n = 6 and 3 n = 8) and three steroids (progesterone, testosterone and oestradiol) have been studied by electrospray mass spectrometry (ES/MS). Mass spectrometric titration experiments have demonstrated differences with regard to selectivity of each p-sulphonato-calix-[n]-arene against the steroids. p-sulphonato-calix-[8]-arene interacts more strongly with oestradiol and p-sulphonato-calix-[6]-arene with progesterone. Studies in which different orifice voltages were applied show that all oestradiol complexes are reduced in signal intensity at 50 V as compared to 20 V, whereas the intensities observed for the testosterone and progesterone complexes do not vary with voltage. Competition experiments confirm the selectivity of the complexation.     

Encapsulation of Luminescent Homoleptic [Ru(dpp)3]2+‐Type Chromophores within an Amphiphilic Dendritic Environment

A new series of homoleptic metallodendrimers has been synthesized through ruthenium‐metal complexation by dendritically modified bathophenanthroline ligands. The presence of hydrophilic oligo(ethylene glycol) groups on the surface of the monodisperse metal complexes enabled the solubilization of all of the fractal species in a wide range of solvents, including water. The specific properties of all of these compounds have been systematically investigated by using photophysical techniques as a function of the generation number. Accordingly, the encapsulation of the highly luminescent [Ru(dpp)₃]²⁺‐type (dpp=4,7‐diphenyl‐1,10‐phenanthroline) core unit within a dendritic microenvironment creates a powerful means to shield the center from dioxygen quenching. This shielding effect, as exerted on the phosphorescent ruthenium‐derived center, is reflected by enhanced emission intensities and extended excited‐state lifetimes that are close to the highest values reported so far, even in an air‐equilibrated aqueous medium. Interestingly, when inspecting the largest dendritic assembly, that is, the third‐generation assembly, significant drops in emission quantum yields and lifetimes are observed. This anomalous behavior has been attributed to the folding of the branches towards the luminescent core.     

Solvent extraction of uranium(VI) by p-tert-butylcalix[n]-arene acetate

The solvent extraction of U(VI) by p-tert-butylcalix[n]-arene acetate (H _n L) (n=4, 6, 8) has been studied. The effects of acidity in aqueous phase and concentration of extractant in organic phase on the distribution ratio were examined. It has been found that the distribution ratio is proportional to [H⁺]⁻² and [H _n L]_(O) and the extracted complex species is UO₂H _n ⁻²L. The equilibrium constants of the extraction reactions have been determined. The reaction mechanism is discussed.     

Unique inclusion behaviour of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetraaminothiacalix[4]-arene towards small organic molecules

Tetraaminothiacalixarene 3, bearing four amino groups instead of the hydroxy groups of p-tert-butylthiacalix[4]arene 2, exhibits inclusion properties different from those of compound 2 towards small organic molecules upon crystallisation from neat solvents or guest solutions. X-ray crystallographic analyses reveal that nitromethane and acetonitrile are included into the cone-shaped cavity of compound 3, as is often seen in inclusion crystals of compound 2, whereas dichloromethane occupies a space between two distal benzene rings of compound 3, adopting a 1,3-alternate conformation. Acetic acid, which forms a dimer, fills a pore surrounded by four host molecules with a pinched cone conformation. Furthermore, guest-free crystals of compound 3 with a 1,3-alternate conformation absorb acetonitrile to give inclusion crystals with the same crystal structure as that obtained by the crystallisation. Thus, compound 3 flexibly changes its conformation according to the structures of guest compounds.     

Molecular recognition of ammonium ion by tetrahomodioxacalix[4]biscrown

The first theoretical study on the conformational features and the complexation behaviors upon ammonium ion binding of tetrahomodioxacalix[4]biscrown-4 has been performed using molecular dynamic simulations and density functional theory. The conformational analyses show that the relative stability and the geometry of the ammonium ion complexes are directly contributed by the number of putative hydrogen bonds between oxygen lone pairs and ammonium hydrogens.     

Calixarenes. 5. Dynamic NMR characteristics of p-tert-butylcalix[4]-arene and p-tert-butylcalix[8]arene

The near identity of the temperature dependent ¹H-NMR spectra of p-tert-butylcalix-[4]- and calix[8]arene in CDCl₃ and bromobenzene-d₅ is shown to be drastically altered in pyridine-d₅, attributable to disruption of intramolecular hydrogen bonding.     

Double template effect in [4 + 4] Schiff base macrocycle formation; an ESI-MS study

The mechanism of self-assembly of a polynuclear complex of a [4 + 4] Schiff base iminomethylenediphenolate macrocycle [BaCu(4)(4 + 4)](2+) via a non-macrocyclic dialdehyde intermediate has been followed using ESI-MS of the reaction solutions. Both assembly of the intermediate and Schiff-base condensation with diamine give rise to single products; formation of the intermediate metallacycle is fast but Schiff-base condensation is much slower. Both intermediate complex and macrocyclic product have been structurally characterised.     

Amphiphilic dipyrrinones: methoxylated [6]-semirubins

Replacing the typical β-alkyl substituents of [6]-semirubin and [6]-oxosemirubin, two intramolecularly hydrogen-bonded bilirubin analogs, with methoxy groups produces amphiphilic dipyrrinones. Synthesized from the respective 9H-dipyrrinones prepared by base-catalyzed condensation of 3,4-dimethoxypyrrolin-2-one with the appropriate pyrrole α-aldehyde, the 2,3-dimethoxy and 2,3,7,8-tetramethoxy analogs of [6]-semirubin are yellow-colored dipyrrinones that form intramolecularly hydrogen-bonded monomers in CDCl₃, as deduced from ¹H NMR NH chemical shifts. They are monomeric in CHCl₃, as determined by vapor pressure osmometry. In contrast, in the solid, X-ray crystallography reveals supramolecular ribbons of intermolecularly hydrogen-bonded (dipyrrinone to dipyrrinone and acid to acid) 2,3,7,8-tetramethoxy-[6]-semirubin. The latter is approximately 20 times more soluble in water than the parent [6]-semirubin with four β-methyl groups.     

Molecular Recognition Properties of Biphen[4]arene

Biphen[n]arenes (n=3, 4) are a new family of macrocyclic hosts. Here, we describe the molecular recognition behavior of hydroxylated biphen[4]arene (OHBP4) for the first time. A series of cationic guests with different sizes and shapes, including quaternary ammonium salts ( 1? PF₆ and 2? PF₆), pyridinium‐based guests ( 3? 2 PF₆– 6? 2 PF₆), and cobaltocenium hexafluorophosphate ( 7? PF₆), were chosen as model guest molecules. OHBP4 exhibits good selectivity towards the 2,7‐dibutyldiazapyrenium bis(hexafluorophosphate) ( 4? 2 PF₆) axle to form a [2]pseudorotaxane‐type complex. In contrast, hydroxylated biphen[3]arene (OHBP3) cannot bind with this big guest. In addition, OHBP4 strongly interacts with adamantane derivative 2? PF₆ and cobaltocenium 7? PF₆, which have tridimensional shape and relatively large size. The association constant of the 7 ⁺?OHBP4 complex in 1:1 (v/v) [D₆]acetone/CD₂Cl₂ solution is up to 3100±300 m ^?1.     

Molecular recognition of organic guest vapor by solid adamantylcalix[4]arene

A series of inclusion compounds prepared by saturation of the solid adamantyl[4]calixarene (host 1) with vaporous organic guests at 298 K was studied by thermal gravimetry and static headspace GC analyses. The sorption isotherms of guests by host 1, the stoichiometry of the guest—host inclusion compounds, and the Gibbs energies of their formation were determined. The data obtained give evidence of the molecular recognition of the guest shape by host 1. Hence, compound 1 can be used in sensors for recognizing volatile organic compounds with no strong hydrogen or donor-acceptor bonds involved.     

Uptake of Hydrocarbons in Aqueous Solution by Encapsulation in Acyclic Cucurbit[n]uril‐Type Molecular Containers

The ability of two water‐soluble acyclic cucurbit[n]uril (CB[n]) type containers, whose hydrophobic cavity is defined by a glycoluril tetramer backbone and terminal aromatic (benzene, naphthalene) sidewalls, to act as solubilizing agents for hydrocarbons in water is described. ¹H NMR spectroscopy studies and phase‐solubility diagrams establish that the naphthalene‐walled container performs as well as, or better than, CB[7] and CB[8] in promoting the uptake of poorly soluble hydrocarbons into aqueous solution through formation of host–hydrocarbon complexes. The naphthalene‐walled acyclic CB[n] container is able to extract large hydrocarbons from crude oil into aqueous solution.     

杯芳烃的研究 I: 三乙酰氧基羟基杯[4]芳烃的合成及其与乙腈形成的包合物的晶体结构

本文报道了25,26,27-三乙酰氧基-28-羟基杯[4]芳烃的合成, 并通过^1H NMR,^1^2C NMR, IR以及元素分析对它进行了表征, 三乙酰氧基羟基杯[4]芳烃在乙腈中重结晶可得到1:1包合物的单晶, X射线结构分析确定它为单斜晶系, 其空间群为P21/n, 属分子间包合物, 在晶体中, 三乙酰氧基羟基杯[4]芳烃呈“内式"的部分锥形构象, 残留羟基处在分子中央, 被苯环和乙酰氧基所包围, 这种构象不利于对残留羟基的进攻。     

New preorganized calix[4]arenes. Part II. Double Schiff-based calix[4]arenes derived from 4,6,10,12,16,18,22,24,25,26,27,28-dodecamethyl-5,11,17,23-tetrahydroxycalix[4]arene

We describe the condensation of an appropriate tetraaldehyde derivative of mesitol calix[4]arene with 1,n-diaminoalkanes to afford double Schiff-base calix[4]arene receptors in the 1,3-alternate conformation.