Hydrophilicity, the major determining factor influencing the solvation environment of protic ionic liquids.

The study of solubility of 4-nitroaniline and its N,N-diethyl derivative in ionic liquids (ILs) of varying water content has shown that it is the interaction between water and the ILs' ions, and not with the solute, that is the most important factor determining the solute's preferential hydration parameter and thus the solvation shell structure.

Unexpected preferential dehydration of artemisinin in ionic liquids.

Thermodynamic measurements (at 298 K) reveal that a crucial step in the extraction process of the key antimalarial drug artemisinin by ionic liquids (ILs), namely, precipitation through the addition of water, is driven by artemisinin dehydration due to the differences in the water's interaction with the bulk ILs, rather than with the artemisinin itself.

New insights into the geometry of resorc[4]arenes: solvent-mediated supramolecular conformational and chiroptical control.

The conformations of inherently chiral resorc[4]arenes were studied by circular dichroism (CD) spectroscopy. Whereas in aprotic solvents the crown conformation (C4) is preferred, protic solvents favor the boat conformation (C2). As a result of electronic coupling of the lowest L(b) state of the resorcinol unit in the resorc[4]arene, the CD spectra show a strong dependence on the conformation of the macrocycle. For the first time the solvent dependence of the CD spectra was qualitatively analyzed and simulated by using theoretical methods. We have thus demonstrated not only that the conformation of the calixarene is dramatically manipulated by the solvent but also that the joint use of chiroptical measurements and theoretical calculations is a powerful and versatile tool for elucidating structural variations in supramolecular chemistry.

Supramolecular chirogenesis with bis-chlorin versus bis-porphyrin hosts: peculiarities of chirality induction and modulation of optical activity.

[structure: see text] The complexation behavior, chirality induction and inversion in the achiral host, a racemic mixture of ethane-bridged bis(zinc octaethylchlorin) (1), and optical activity modulation in the chiral hosts, enantiopure 1(R) and 1(S), upon interaction with chiral and achiral amine guests have been investigated by means of the UV-vis, CD, and (1)H NMR techniques and compared with the corresponding spectral data of the bis-porphyrin analogue. It was found that the chirogenesis pathway is strongly dependent upon the structures of both major components (hosts and guests) of these supramolecular systems. Particularly, the distinct orientation of electronic transitions in the chlorin chromophores arisen from the reduced pyrrole ring, which makes it radically different from that of the porphyrin chromophores, and the size of the guest's substituents lead to the remarkable phenomenon of chirality induction-inversion in racemic 1 originating from the process of asymmetry transfer from enantiopure guests of the same homologous type and absolute configuration. This surprising chirogenic behavior is found to be in a sharp contrast to that observed in the analogous porphyrin-based systems. Furthermore, these structural and electronic phenomena also account for the effective optical activity quenching of enantiopure 1(R) and 1(S) upon interaction with chiral and with achiral amines, which results in formation of supramolecular complexes of opposite chirality.

Chiral Bis-chlorin: enantiomer resolution and absolute configuration determination.

[structure: see text] A racemic mixture of the ethane-bridged bis(zinc octaethylchlorin) was successfully resolved for the first time to yield two enantiomers that exhibit substantial CD signals in the regions of chlorin B and Q transitions. The absolute configuration of the corresponding enantiomers was assigned and the origin of its high optical activity was rationalized through a combined spectral, crystallographic, and theoretical analysis.

Origin, control, and application of supramolecular chirogenesis in bisporphyrin-based systems.

The rationalization of various aspects of the mechanism of chirality induction in supramolecular assemblies based upon the complexes formed between an ethane-linked bisoctaethylporphyrin and chiral ligands is described. The influence of various controlling factors such as bonding strength, host-guest steric interactions, equilibria and thermodynamic parameters, temperature and solvent effects, role of the center metal ion, stoichiometry, and phase transition on the chirality induction processes have been investigated, and the results and implications are discussed. As a result of such detailed understanding, it is possible to employ this bisporphyrin system as an effective chirality sensor for the determination of absolute configuration.

Supramolecular chirogenesis in zinc porphyrins: interaction with bidentate ligands, formation of tweezer structures, and the origin of enhanced optical activity.

The complexation behavior, binding properties, and spectral parameters of supramolecular chirality induction in the achiral host molecule, syn (face-to-face conformation) ethane-bridged bis(zinc porphyrin), upon interaction with chiral bidentate guests (diamines and amino alcohols) have been studied by means of UV-vis, CD, fluorescence, (1)H NMR, and ESI MS techniques. It was found that the guest structure plays a decisive role in the chirogenesis pathway. The majority of bidentate ligands (except those geometrically unsuitable) exhibit two major equilibria steps: the first guest ligation leading to formation of the 1:1 host-guest tweezer structure (K(1)) and the second guest molecule ligation (K(2)) forming the anti bis-ligated species (1:2). The second ligation is much weaker (K(1) >> K(2)) due to the optimal geometry and stability of the 1:1 tweezer complex. The enhanced conformational stability of the tweezer complex ensures an efficient chirality transfer from the chiral guest to the achiral host, consequently inducing a remarkably high optical activity in the bis-porphyrin.

Absolute asymmetric photoreactions of aliphatic amino acids by circularly polarized synchrotron radiation: critically pH-dependent photobehavior.

The absolute asymmetric photoreaction (AAP) of racemic aliphatic amino acids, such as alanine (Ala) and leucine (Leu), by left- and right-handed circularly polarized light (l- and r-CPL) irradiation was investigated in aqueous solutions at various pHs, by using the Onuki-type polarizing undulator installed in an electron storage ring. The magnitude of the optical purity (op) generated and the enantiomer-enriching mechanism operative in the AAP were found to be entirely dependent on the ionic state (and thus pH) of the amino/carboxylic acid moieties. At pH 1, the op of Ala and Leu determined by circular dichroism (CD) spectral measurement gradually developed with CPL irradiation, according to Kagan's equation. In contrast, irradiation at pH 7 gave op's much smaller than the theoretical values predicted by Kagan's equation. However, it turned out that the photodecomposition at pH 7 produces the corresponding alpha-hydroxycarboxylic acids stereoselectively, the CD sign of which is just opposite to that of the remaining amino acid, thus affording the apparently small op. It is concluded that, irrespective of solution pH, the AAP of amino acid proceeds upon CPL irradiation. At pH 1, the photodecomposition of valine, Leu, and isoleucine occurs via a Norrish type II mechanism, which is also applicable to other amino acids possessing a gamma-hydrogen. In the case of amino acids lacking a gamma-hydrogen, such as glycine and Ala, the photodecomposition mechanism is a photodeamination/hydroxylation and a Norrish type I reaction. At pH 7, the main photoproducts were ammonia and alpha-hydroxycarboxylic acids that were produced via photodeamination.