桝 飛雄真

Abstract Here, an unprecedented phenomenon in which 7‐coordinate lanthanide metallomesogens, which align via hydrogen bonds mediated by coordinated H₂O molecules, form micellar cubic mesophases at room temperature, creating body‐centered cubic (BCC)‐type supramolecular spherical arrays, is reported. The results of experiments and molecular dynamics simulations reveal that spherical assemblies of three complexes surrounded by an amorphous alkyl domain spontaneously align in an energetically stable orientation to form the BCC structure. This phenomenon differs greatly from the conventional self‐assembling behavior of 6‐coordinated metallomesogens, which form columnar assemblies due to strong intermolecular interactions. Since the magnetic and luminescent properties of different lanthanides vary, adding arbitrary functions to spherical arrays is possible by selecting suitable lanthanides to be used. The method developed in this study using 7‐coordinate lanthanide metallomesogens as building blocks is expected to lead to the rational development of micellar cubic mesophases.

The metal–insulator transition induced by the gate electric field in the charge order phase of the α-(BEDT-TTF)2I3 single-crystal field-effect transistor (FET) structure was clearly observed near the phase transition temperature. An abrupt increase in the electrical conductance induced by the applied gate electric field was evident, which corresponds to the partial dissolution of the charge order phase triggered by the gate electric field. The estimated nominal dissolved charge order region (i.e., the gate-induced metallic region) was overestimated in 130–150 K, suggesting additional effects such as Joule heating. On the other hand, in the lower temperature region below 120 K, the corresponding dissolved charge order was several monolayers of BEDT-TTF, suggesting that it is possible to dissolve the charge order phase within the bistable temperature region.

The seven-coordinate Ho(III) aqua-tris(dibenzoylmethane)(DBM) complex, referred to as Ho-(DBM)3·H2O, was first reported in the late 1960s. It has a threefold symmetric structure, with Ho at the center of three dibenzoylmethane ligands and hydrogen-bonded water to ligands. It is considered that the hydrogen bonds between the water molecule and the ligands surrounding Ho play an important role in the formation of its symmetrical structure. In this work, we developed new force-field parameters for classical molecular dynamics (CMD) simulations to theoretically elucidate the structure and dynamics of Ho-(DBM)3·H2O. To develop the force field, structural optimization and molecular dynamics were performed on the basis of ab initio calculations using the plane-wave pseudopotential method. The force-field parameters for CMD were then optimized to reproduce the data obtained from ab initio calculations. Validation of the developed force field showed good agreement with the experimental crystalline structure and ab initio data. The vibrational properties of water in Ho-(DBM)3·H2O were investigated by comparison with bulk liquid water. The vibrational motion of water was found to have a characteristic mode originating from stationary rotational motion along the c-axis of Ho(III) aqua-tris(dibenzoylmethane). Contrary to expectations, the hydrogen-bond dynamics of water in Ho-(DBM)3·H2O were found to be almost equivalent to those of bulk liquid water except for librational motion. This development route for force-field parameters for CMD and the establishment of water dynamics can advance the understanding of water-coordinated metal complexes with high coordination numbers such as Ho-(DBM)3·H2O.

Tetraalkoxylated diphenylureas U-3,4-Scit and U-3,4-raccit were synthesized from chiral and racemic citronellyl bromides as starting materials, respectively. To prepare pyroelectric crystals, these two compounds were slowly cooled from their molten states. Although the two compounds have very similar molecular structures, they exhibited quite different electric-field responsiveness. U-3,4-Scit spontaneously polarized during the crystallization process, and almost no polarization switching was observed. On the other hand, U-3,4-raccit exhibited polarization switching in its crystalline state at a high-temperature range, and the polarization direction could be fixed by cooling the crystal to room temperature while applying a direct current voltage. This flexibility occurs because the alkyl chain parts in the crystal are disordered. These pyroelectric thin films are promising materials, as they function in a polycrystalline state without poling treatment.

Holmium (Ho) is a lanthanide element with a high magnetic moment. Here, we create an amorphous metal-organic framework (MOF) that has no long-range periodic order but retains the basic components of MOF by using isophthalic acid as an organic linker and Ho as a metal species. The resulting spherical Ho-MOF particles disperse well in a solvent and exhibit excellent magnetic properties in response to magnets. Since Ho has almost no coloring, Ho-MOF particles are a colorless magnetic material, unlike conventional iron oxide particles. Taking advantage of the colorless property, the selective adsorption of dyes on Ho-MOF particles can be easily visually confirmed by magnetically separating the particles. In addition, present versatile processes that enable adaptation of lanthanide elements other than Ho enable the development of colorless multifunctional MOF particles.

[Cu(4,4'-bipyridine)2(BF4)2] (ELM-11), an elastic layer-structured MOF (metal-organic framework), is expected to be a sophisticated CO2 reservoir candidate because of its high capacity and recovery efficiency for CO2 sorption. While ELM-11 shows a unique double-step gate sorption for CO2 gas, the dynamics of the structural transition have not yet been clarified. In this study, the dynamics of the 4,4'-bipyridine linkers and the BF4- anions were studied by determining 1H spin-lattice relaxation times (T1). The ELM-11 structural transition accompanying CO2 sorption was also examined through the CO2 uptake dependence of the 1H spin–spin relaxation time (T2), in addition to T1. In its closed form, the temperature dependence of the 1H T1 of ELM-11 was analyzed by considering the contributions of both paramagnetic and dipolar relaxations, which revealed the isotropic reorientation of BF4- and the torsional flipping of the 4,4'-bipyridine moieties. The resultant activation energy of 32 kJ mol-1 for the isotropic BF4− reorientation is suggestive of strong (B-F...Cu2+) interactions between Cu(II) and the F atoms in BF4−. Furthermore, the CO2 uptake dependence of T1 was found to be dominated by competition between the increase in the longitudinal relaxation time of the electron spins and the decrease in the spin density in the unit cell.

© 2019 The Royal Society of Chemistry. Calix[3]aramide-based cylindrical macrocycles were synthesized by the one-step amide coupling reaction of a monomer containing two meta-alkylaminobenzoic acid units linked by para-phenylene bridges. The major products included a meso-form and an enantiomeric pair, with stereochemistry derived from the direction of the amide bonds and their fixed conformation. Mirror-image ECD, VCD, and CPL spectra were observed in the enantiomeric pair and the absolute structure was determined by comparing measured and calculated ECD and VCD spectra.

A neutral bis(imidazolidine)pyridine (PyBidine)-CoCl2 complex showed catalytic activity for the Michael reaction of malonates with nitroalkenes. The results indicated that a weak amine base aided enolate formation from the neutral complex, in which the N-H proton of the imidazolidine ligand played a significant role.

A phosphoiminoBINOL ligand was designed to form a dinuclear metal complex that could hold a malononitrile molecule. The dinuclear bis(phosphoimino)binaphthoxy-Pd2(OAc)2 complex catalyzed a double Mannich reaction of N-Boc-imines with malononitrile to give chiral 1,3-diamines with high enantioselectivity. The rational asymmetric catalyst, which smoothly introduces the first coupling product to the second coupling reaction while avoiding the reverse reaction, facilitates the over-reaction into a productive reaction process.

Copyright © 2018 American Chemical Society. A coculture method with a pathogenic actinomycete of the genus Nocardia and an animal cell line was designed to reconstruct and emulate the initial infection state, and a new cyclic nonapeptide, named nocarjamide (1), was obtained by coculture of Nocardia tenerifensis IFM 10554T and the mouse macrophage-like cell line J774.1 in a modified Czapek-Dox medium. Nocarjamide (1) exhibited Wnt signal-activating effects.

Macrocyclization of a stable two-turn helical aromatic pentamide, that is, an object with diverging ends that are not prone to cyclization, was made possible by the transient introduction of disruptors of helicity in the form of acid-labile dimethoxybenzyl tertiary amide substituents. After removal of the helicity disruptors, NMR, X-ray crystallography, and computational studies show that the macrocycle possesses a strained structure that tries to gain as high a helical content as possible despite being cyclic. Two points of disruption of helicity remain, in particular a cis amide bond. This point of disruption of helicity can propagate along the cycle in a fluxional manner according to defined trajectories to produce ten degenerate conformations.

N-Alkylbenzanilides generally exist in cis conformation both in the crystalline state and in various solvents, and this cis conformational preference can be utilized to construct dynamic helical oligoamides. Here, we synthesized the pyrrole-containing amides 2-5 and their oligomers 6-8 and examined their conformations in the crystalline state and in solution. All the N-methylated amides showed cis conformational preference in solution, but the ratio of the cis isomer was decreased when the amide bond was attached at the 4-position of the pyrrole ring, probably because the destabilization of the trans conformer due to electronic repulsion between the pyrrole π electrons and the amide carbonyl lone-pair electrons is reduced due to the small torsion angle between the 5-membered N-pyrrole and the amide bond. In the crystalline state, N-methylated amides showed cis structure, except for compound 5, and cis conformational preference was observed for the pyrrole amides. The CD spectra of oligoamides 15-18 bearing chiral N-substituents were consistent with the presence of dynamic and well-defined chiral foldamers, which were structurally distinct from N-alkylated poly(p-benzamide)s 1.

The morphology and stability of amorphous nanoparticles of glibenclamide (GLB) prepared by the antisolvent method using different methods of adding hypromellose (HPMC) were evaluated. Nano-A was prepared by the injection of a dimethyl sulfoxide (DMSO) solution of GLB into the HPMC solution, whereas nano-B was obtained by the injection of a DMSO solution of GLB and HPMC into water. Cryogenic transmission electron microscopy, field-emission scanning electron microscopy, and field-emission transmission electron microscopy, including energy dispersive X-ray spectrometry, revealed that the particles of the nano-A and nano-B samples are hollow spheres and nonspherical nanoparticles, respectively. Powder X-ray diffraction and solid-state NMR measurements showed that GLB is present in an amorphous state in both nano-A and nano-B. The weight ratios of HPMC in the GLB/HPMC nanoparticles were 11 and 16% for nano-A and nano-B, respectively, as determined by solution-state NMR. The glass transition temperatures (Tg) of nano-A and nano-B evaluated using differential scanning calorimetry were lower by about 10 °C compared to that of amorphous GLB, presumably because of a Tg confinement effect and the surface coverage and mixing of HPMC, as suggested by the inverse gas chromatography experiment. GLB crystallization during storage was suppressed more strongly in nano-B than nano-A, owing to the higher amount of HPMC and the higher miscibility between GLB and HPMC. It is suggested that the diffusion rate of the solvent during nanoprecipitation determined the nanoparticle properties. In nano-A, the precipitation of GLB first occurred at the outer interface because of the rapid diffusion of the solvent. Thus, hollow spherical particles with HPMC preferentially located near the surface were formed. On the other hand, the diffusion of the solvent in nano-B was suppressed because of the presence of HPMC, yielding small nonspherical nanoparticles with a high miscibility of GLB and HPMC.

Mycoplasma pneumoniae expresses β-glycolipids (β-GGLs) in cytoplasmic membranes, which possess a unique β(1 → 6)-linked disaccharide epitope, which has high potential in biochemical and medicinal applications. In the present study, a series of β-GGLs homologues with different acyl chains (C12, C14, C16, and C18) were prepared from a common precursor. An ELISA assay using an anti-(β-GGLs) monoclonal antibody indicated that the synthetic homologues with long acyl chains had greater diagnostic potential in the order C18 &gt C16 &gt C14 &gt C12. Toward a simultaneous detection of natural glycolipids by mass spectrometry (MS), a deuterium-labeled C16 homologue (β-GGL-C16-d3) was prepared and applied as an internal standard for a high-resolution electrospray ionization MS (ESI-MS) analysis. The ESI-MS analysis was used to identify and quantify acyl homologues (C16/C16, C16/C18, and C18/C18) of β-GGL-C16 in cultured M. pneumoniae. A β-GGLs homologue with a 1,2-diacetyl group (C2) was also prepared as a “water soluble” glycolipid homologue and characterized by 1H NMR spectroscopy. We envisage that each of these chemosynthetic homologues will provide promising approaches to solve medical and biological problems associated with mycoplasma infectious diseases (MIDs).

The effect of the side chain chiral center position on the secondary structure of oligomers and polymers of N-substituted 4-aminobenzoic acid was studied. Monomer 1 was prepared from L-alanine methyl ester hydrochloride in seven steps. The poly(p-benzamide) having an α-substituted side chain at the nitrogen atom (α-Me-PA) was obtained from the polymerization of 1 with triethylsilane, CsF, and 18-crown-6 in THF. The circular dichroism (CD) studies in solution demonstrated that α-Me-PA adopted a right-handed helical conformation in protic polar solvents, such as water and methanol, and a random structure in chloroform, indicating that solvophobic interactions played an important role in the helical folding of α-Me-PA. The tetramer of (S)-4-(sec-butylamino)benzoic acid was synthesized as a model compound of α-Me-PA. The single crystal X-ray analysis of the tetramer revealed that the right- and left-handed helical molecules existed in a one-to-one ratio in the crystal, and that the screw pitch of the right-handed helix was shorter than the left-handed helix.

Two excited-state intramolecular proton transfer (ESIPT) active benzimidazole derivatives (1 and 2) were synthesized by acid-catalyzed intramolecular cyclization. The steady-state fluorescence spectrum in THE revealed that ring-fused derivative 1 exhibits a dual emission, namely, the major emission was from the K* (keto) form (ESIPT emission) at 515 nm with a large Stokes shift of 11 100 cm(-1) and the minor emission was from the E* (enol) form at below 400 nm. In contrast, the normal emission from the E* form was dominant and the fluorescence quantum yield was very low (Phi similar to 0.002) for nonfused derivative 2. The time-resolved fluorescence spectroscopy of 1 suggested that ESIPT effectively occurs due to the restricted conformational transition to the S-1-T-ICT state, and the averaged radiative and nonradiative decay rate constants were estimated as < k(f)> = 0.15 ns(-1) and < k(nr)> = 0.60 ns(-1), respectively. The fluorescence emission of 1 was influenced by the measurement conditions, such as solvent polarity and basicity, as well as the presence of Lewis base. The ESIPT process and solvatochromic behavior were nicely reproduced by the DFT/TDDFT calculation using the PCM model. In the single-crystal fluorescent spectra, the ESIPT emissions were exclusively observed for both fused and nonfused compounds as a result of hydrogen-bonding interactions.

Here, aiming to adopt the phenyl-perfluorophenyl interaction to regulate molecular alignment and arrangement for crystal engineering, we examined and compared in detail the crystal structures of N,N'-diphenylurea compounds 1-6. We found that phenyl-perfluorophenyl interaction greatly influenced the intermolecular arrangement in the crystal, and we were able to prepare a cocrystal of 1 and 2, in which the molecules were alternately arranged under the control of the phenyl-perfluorophenyl interaction. This arrangement was driven by the asymmetric geometry of the hydrogen bonds in the cocrystal (1.2), in which 2, bearing two perfluorophenyl groups, worked as a better hydrogen bond donor. In contrast, NH connected to the phenyl group in 3 proved to be a better hydrogen bond donor due to the intramolecular resonance effect. N,N'-Dimethylated derivatives, 4-6, existed in cis-cis form in the crystal. Antiparallel carbonyl carbonyl arrangements were observed in 4 and 6, while an unexpected carbonyl perfluorophenyl interaction was observed in the crystal of 5. These findings will be helpful in the design of diphenylurea-based functional molecules, especially for solid-state application.

Europium(III)-phosphine oxide porous coordination polymers (Eu-PCPs) constructed from Eu(OTf)(3) and tris(4-(4'-carboxylphenyl) phenyl) phosphine oxide as ligands are reported. X-Ray diffraction data of Eu-PCPs are collected at 273 K with synchrotron radiation. The europium complex is shown to crystallize in the centrosymmetric orthorhombic space group Pcca. The Eu atom is surrounded by eight neighboring oxygen atoms from six ligands and a coordinated DMF molecule. Furthermore, the two Eu centers are quadruply bridged by four carboxylates. They exhibit an infinite three-dimensional structure that incorporates an open pore structure, which is thermally robust and has an N-2 Brunauer-Emmett-Teller surface area of 58.5 m(2) g(-1) and a micropore volume of 0.756 cm(3) g(-1). Excitation of the materials led to five sharp emission peaks arising from the D-5(0) -> F-7(J) transitions (J = 0, 1, 2, 3 and 4). The absolute quantum yield of Eu-PCPs is determined as 22% at room temperature. In addition, exposure of single crystals of Eu-PCPs to H2O vapor causes attenuation of the luminescence intensity. This process involves a single-crystal- to-single-crystal transformation. In the crystal structures of the Eu-PCPs, the ligand exchange from DMF to H2O, which acts to quench the lanthanide luminescence, is directly observed.

The title compounds, C16H14O2S2 and C16H14O3S, which are monomeric models (models D and E) for a polythionoester and a poly(ester-co-thionoester), respectively, crystallize in the space group P21/c and are isostructural with each other. The molecule in each crystal is located on an inversion centre and has an all-trans structure. The asymmetric unit comprises one half-molecule. In the crystal, there are intermolecular C· · ·S contacts [3.391 (3) and 3.308 (3) Å for models D and E, respectively] and C-H· · ·· π interactions, which form a layer structure parallel to the bc plane. The carbonyl and thiocarbonyl groups of the model E compound are each disordered over two equivalent sites about the inversion centre with equal occupancies.

Fused imidazole monomers (1b, 1li, and 2b) having the octyl group were synthesized by the microwave-assisted intramolecular direct arylation, which were subjected to the cross coupling polymerization. For obtaining g-conjugated polymers with better solubility, fused imidazole monomers (si-1b and si-3b) having the bulky trisiloxane-terminated decyl chain were likewise synthesized and polymerized. On the basis of absorption and emission spectra of obtained pi-conjugated polymers in conjunction with the X-ray crystal structure theoretical calculation, the fused structure and coupling partner were found to affect the optical properties in CHCl3 solution as a result of steric and electronic factors. The spectroscopic measurements in film revealed that the bulky trisiloxane group helps conjugated, polymers to form the rc-stacked structure upon thermal annealing. The proton doping experiment was also carried out to find out that the protonation of imidazole nitrogen results in the different peak shift depending on the comonomer structure.

Three dithienobenzimidazole derivative monomers (M1, M2, and M3) were prepared, where M3 was obtained by the oxidation of M1 and identified by the X-ray crystallographic analysis. pi-Conjugated homopolymers (P1-0, P2-0, and P3-0) and copolymers (P1-2, P3-1, and P3-2) were synthesized by the palladium-catalyzed coupling polymerizations of M1, M2, and M3. The absorption spectra of the reference compounds (fused R1 and non-fused R2), in conjunction with the optimized ground state structure, certified the importance of the fused dithienobenzimidazole skeleton to increase the effective conjugation length of the polymers. On the basis of the absorption and emission spectra of the pi-conjugated polymers in CHCl3, the influence of the thiophene-S, S-dioxide as well as the comonomer structure were investigated to find out that P3-0 and P3-2 exhibited peak maxima at the relatively longer wavelength region due to the donor-acceptor interaction. In addition, the protonation of the imidazole imine group further tuned the optical properties of the it-conjugated polymers by promoting the charge transfer interaction along the polymer main chain, which was supported by the theoretical calculations in detail. (C) 2016 Elsevier Ltd. All rights reserved.

Bidentate organic molecules with imidazole or benzimidazole moieties connected to a rigid 1,3-diphenyladamantane spacer are simple and unique building blocks that facilitate the assembly of supramolecular architectures in the solid state via metal-coordination. Single-crystal X-ray analysis revealed that the complexation of bidentate ligand-bearing imidazole moieties with cobalt(II) or cadmium(II) ions in methanol/chloroform produced complexes that showed doubly interpenetrated two-dimensional (2D) sheets through the formation of coordination bonds between the cobalt or cadmium metal centers and the nitrogen atoms of the imidazole groups. In the complexation of another ligand bearing a bulky benzimidazole group with cobalt(II) ion generated in methanol/chloroform, extended zigzag one-dimensional (1D) chains were formed, indicating that the molecular shape and bulkiness of the ligand design are crucial in the control of coordination polymers. The crystallization solutions were subjected to cold-spray ionization mass spectrometry (CSI-MS), and ion peaks derived from complexes with metal-ligand 1:2 and 1:1 were observed in complexation with ligands bearing the imidazole and benzimidazole moieties, respectively. The metal-ligand ratio in the CSI-MS analysis was identical to that found in the single-crystal X-ray analysis of an independent molecule. In addition, coordination oligomers with large molecular weight were detected as part of the obtained coordination polymers observed by CSI-MS/MS.

(S,S)-Diphenylethylenediamine-derived bis(imidazolidine)pyridine (PyBidine)-Ni(OAc)(2) complex catalyzed the asymmetric Michael/aldol reaction of methyleneindolinone and thiosalicylaldehyde to produce (2'R,3S,4'R)-thiochromanyl-spirooxindole having three contiguous stereogenic centers.

A range of bromothiopheneS reacted with lithium boranato(tert-butyl)methylphosphide in the absence of transition metal catalysts under mild conditions to provide the same 2,5-disubstituted and 2-monosubstituted products regardless of the substitution patterns of the starting bromothiophenes.

A new bis-aporphine alkaloid, cerasoidine (1), was isolated from the root extract of Polyalthia cerasoides together with the known bis-aporphine bidebiline E (2) during screening for compounds with Wnt signal inhibitory activities. The structure of cerasoidine (1) was established by X-ray analysis and shown by chiral HPLC analyses and electronic circular dichroism to be a 57:43 mixture of R(-)- and S(+)-atropisomers. Bidebiline E (2) exhibited inhibition of transcriptional activity of TCF/beta-catenin with an IC50 value of 20.2 mu M and was also found to inhibit Wnt signaling by decreasing nuclear beta-catenin.

The reaction of 2-(2-alkynylphenyl)benz[d]imidazoles with molecular iodine constructed 5- and 6 -membered rings as novel organic salts in high yield. The constituted number of ring systems was influenced by the substituent at the triple bond: 6-membered rings were formed from compounds bearing aryl substituents, whereas 5-membered ones were obtained from compounds with hydrogen or alkyl substituents. The products were obtained with triiodide as a counteranion; however, compounds with iodide were also obtainable under certain conditions. We also revealed that they had an iodine iodine interaction included in halogen bonding between an iodo moiety of the cation and a triiodide or iodide of the counteranion. The iodine iodine interaction was formed with greater preference than the electrostatic interaction between the cationic atom and triiodide or iodide.

The incorporation of flexible aliphatic units into otherwise rigid aromatic foldamer sequences may result in different outcomes. The flexible units may have conformational preferences of their own that can be expressed orthogonally to those of the aromatic units. Alternatively, the latter may dictate their folding behavior onto the former. Hybrid aliphatic-aromatic peptidic oligomers combining oxazole-based (O) and quinoline-based (Q) amino acids have been synthesized, and their folding behavior has been investigated in solution by NMR spectroscopy and CD spectroscopy, and in the solid state by Xray crystallography. Sequences based on the OQQ repeat motif were shown to fold into a canonical aromatic helix motif dominated by the preferences of the quinoline, whereas sequences based on OQ repetitions preferred to fold into a herringbone helix in which the conformational preference of the oxazole units is also expressed.

The effect of an applied gate electric field on the charge-order phase in beta-(BEDT-TTF)(2)PF6 single-crystal field-effect transistor structure was observed at around room temperature by technical improvement with respect to sample preparation and electrical measurements. A relatively slight but systematic increase of the electrical conductance induced by the applied gate electric field and its temperature dependence was observed at around the metal-insulator transition temperature (T-MI). The temperature dependence of the modulated electrical conductance demonstrated that T-MI was shifted toward the lower side by application of a gate electric field, which corresponds to partial dissolution of the charge-order phase. The thickness of the partially dissolved charge order region was estimated to be several score times larger than the charge accumulation region.

Two adamantane-bridged tripodal trisimidazolium or trisbenzimidazolium salts were designed as C-3v-symmetrical tricarbene ligands and synthesized in good yields. The reaction of the tripodal trisazolium salt precursors with silver oxide provided trisilver hexacarbene complexes bearing a three-dimensional framework. Multinuclear NMR spectroscopy and mass spectrometry data showed that the complexes were symmetric structures of two tricarbene ligands, three metal ions, and three counter anions. X-ray crystallographic analyses revealed that both complex cations adopted a highly twisted conformation. The complex cations built from the trisimidazolium salts were arranged into columnar structures through CH/pi interactions, which were assembled into a three-dimensional network structure by intermolecular CH/F interactions via hexafluorophosphate anions. The complex cations generated from the trisbenzimidazolium salts were aligned into columnar structures, which were arranged into a network structure through CH/pi interactions. Solvents and counter anions were accommodated in the spaces of the crystalline lattices.

Fused pi-conjugated imidazolium compounds bearing two or three long alkoxy chains and various counter anions were systematically prepared following our reported synthetic route. On the basis of DSC measurements and POM observations, the combination of three alkoxy chains longer than the dodecyl group and moderately coordinating anions was important to obtain an enantiotropic mesophase. VT-XRD measurements coupled with a single crystal X-ray structure of a model compound revealed a hexagonal columnar structure supported by ionic interactions. The regularity of the self-organized nanostructure was governed by the alkoxy chain length and the coordinating ability of the counter anion. In the solution state, UV-vis and fluorescence peak maxima were influenced by the number of alkoxy chains and independent of the chain length and anion character. On the contrary, the alkoxy chain length and the coordinating ability of the counter anion had a large impact on the fluorescence spectra in the solid state. A longer wavelength emission at around 560 nm was observed for compounds with the highly regular hexagonal columnar structure. From the result of fluorescence lifetime measurements, the interaction between fused pi-conjugated imidazolium cations was suggested.

A first generation of fluorine-free lithium and sodium salts based on the concept of pseudo-delocalized anions has been synthesized with both high purity and yield using water as the solvent in the reaction medium. The salts have been fully characterized by Raman and FT-IR spectroscopies, thermogravimetry, and X-ray crystallography to reveal both basic properties in terms of thermal stability and solubility as well as the local, mainly ion-ion interaction dictated, coordination details and by ionic conductivity and electrochemical stability window measurements as aqueous electrolytes. Together a picture is created of the salts' promise as components in electrolytes - primarily aiming at application in low voltage fluorine-free aqueous lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs).

Cyclic triamides 4 bearing amidino groups at the meta position of the phenyl rings were synthesized, and their conformational properties in the crystal and in solution were examined. Compound 4a exists as a capsule-type dimer of the enantiomers with a bowl-shaped syn conformation in the crystal state. Compound 4 exists mainly in the syn form in solution, and chiral induction was observed upon addition of a chiral acid to a solution of 4a. Chirality 27:487-491, 2015. (c) 2015 Wiley Periodicals, Inc.

Chiral bis(imidazolidine)-derived NCN-rhodium complexes ([PhBidine-RhX2] and [tBu-PhBidine-RhX2]) were prepared by a CH insertion method, and the structures were unequivocally determined by X-ray crystallographic analysis. The [tBu-PhBidine-Rh(OAc)(2)] complex smoothly catalyzed an asymmetric Mannich reaction of malononitrile with N-Boc imines to give products in up to 94% ee, which are useful for the synthesis of chiral -amino acids.