Supramolecular Handshakes: Characterization of Urea-Carboxylate Interactions Within Calixarene Frameworks.

The research of molecular capsules offers high application potential and numerous benefits in various fields. With the aim of forming supramolecular capsules which can be reversibly assembled and dissociated by simple external stimuli, we studied interactions between calixarenes containing urea and carboxylate moieties. To this end two ureido-derivatives of p-tert-butylcalix[4]arene comprising phenylureido-moieties and diacetate-calix[4]arenes were prepared. The binding of acetate by ureido-derivatives of calixarene in acetonitrile was characterized, revealing high affinity of ureido-calixarenes for carboxylates. This suggested high potential for uniting the complementary calix[4]arenes via H-bonds between carboxylic groups and urea moieties. The assembly of calixarenes was examined in detail by means of UV, 1H NMR, ITC, DOSY, MS, and conductometry providing insight in the structure-stability relationship. The tetraureido-calixarene derivative formed the most stable heterodimers with diacetate-calix[4]arenes featuring practically quantitative association upon mixing the two calixarene counterparts. The possibility of controlling the formation of the heterodimer by protonating the carboxylates, thereby hindering the interactions critical for capsule assembly, was investigated. Indeed, the reversibility of breaking and re-forming the heterodimer by addition of an acid and base to the solution containing urea- and carboxylate-derivative calix[4]arene was demonstrated using NMR spectroscopy.

Protonation and anion-binding properties of aromatic sulfonylurea derivatives.

In this work the anion-binding properties of three aromatic sulfonylurea derivatives in acetonitrile and dimethyl sulfoxide were explored by means of NMR titrations. It was found that the studied receptors effectively bind anions of low basicity (Cl-, Br-, I-, NO3 - and HSO4 -). The stoichiometry of the complexes with receptors containing one binding site was 1 : 1 exclusively, whereas in the case of the receptor containing two sulfonylurea groups 1 : 2 (receptor : anion) complexes were also detected in some cases. The presence of strongly basic anions (acetate and dihydrogen phosphate) led to the deprotonation of the sulfonylurea moiety. This completely hindered its anion-binding properties in DMSO and only proton transfer occurred upon the addition of basic anions to the studied receptors. In MeCN, a complex system of equilibria including both ligand deprotonation and anion binding was established. Since ionisation of receptors was proven to be a decisive factor defining the behaviour of the sulfonylurea receptors, their pK a values were determined using several deprotonation agents in both solvents. The results were interpreted in the context of receptor structures and solvent properties and applied for the identification of the interactions with basic anions.

Acid-base properties of phosphoric and acetic acid in aprotic organic solvents - A complete thermodynamic characterisation.

Knowledge regarding the acid-base behaviour in non-aqueous media has remained relatively scarce in spite of its importance for many aspects of chemistry. The research presented in this work fills some of particularly important gaps in the corresponding thermodynamic data. We report on a detailed study of acid-base properties of dihydrogen phosphate and acetate in aprotic organic solvents (acetonitrile, dimethyl sulfoxide, and dimethylformamide). It was found that several processes, i.e. protonation, homoassociation, and dimerisation play important roles in defining the basicity of these widely important anions. In the case of dihydrogen phosphate, formation of higher homoassociates (two anions, one acid molecule and vice versa) was detected, whereas acetate formed only simple homoassociates of 1:1 stoichiometry. The dimerisation of dihydrogen phosphate and acetic acid were confirmed to be important processes as well. The thermodynamics of the above mentioned reactions was characterised in detail by means of various experimental methods: ITC, spectrophotometry, NMR-spectroscopy, and conductometry. Reliable equilibrium constants and other thermodynamic reaction functions were determined. The obtained results were discussed in terms of hydrogen bonding potential of the anions and their conjugated acids, as well as solvent properties, i.e. their ability to solvate the species involved in the studied processes.

Bis(amino acid) oxalyl amides as ambidextrous gelators of water and organic solvents: supramolecular gels with temperature dependent assembly/dissolution equilibrium.

Bis(LeuOH) (1a), bis-(ValOH) (2a) and bis(PhgOH) (5a) (Phg denotes (R)-phenylglycine) oxalyl amides are efficient low molecular weight organic gelators of various organic solvents and their mixtures as well as water, water/DMSO, and water/DMF mixtures. The organisational motifs in aqueous gels are dominated primarily by lipophilic interactions while those in organic solvents are formed by intermolecular hydrogen bonding. Most of the gels are thermoreversible and stable for many months. However, 2a forms unstable gels with organic solvents which upon ageing transform into variety of crystalline shapes. For some 1a/alcohol gels, a linear correlation between alcohol dielectric constants (epsilon) and gel melting temperatures (Tg) was found. The 1H NMR and FTIR spectroscopic investigations of selected gels reveal the existence of temperature dependent network assembly/dissolution equilibrium. In the 1H NMR spectra of gels only the molecules dissolved in entrapped solvent could be observed. By using an internal standard, the concentration of dissolved gelator molecules could be determined. In FTIR spectra, the bands corresponding to network assembled and dissolved gelator molecules are simultaneously present. This enabled determination of the Kgel values by using both methods. From the plots of InKgel versus 1/T, the deltaHgel values of selected gels have been determined (-deltaHgel in 10-36 kJ mol(-1) range) and found to be strongly solvent dependent. The deltaHgel values determined by 1H NMR and FTIR spectroscopy are in excellent agreement. Crystal structures of 2a and rac-5a show the presence of organisational motifs and intermolecular interactions in agreement with those in gel fibres elucidated by spectroscopic methods.