Proton Conduction at High Temperature in High-Symmetry Hydrogen-Bonded Molecular Crystals of RuIII Complexes with Six Imidazole-Imidazolate Ligands

A new H-bonded crystal [Ru^III(Him)₃(Im)₃] with three imidazole (Him) and three imidazolate (Im⁻) groups was prepared to obtain a higher-temperature proton conductor than a Nafion membrane with water driving. The crystal is constructed by complementary N−H⋅⋅⋅N H-bonds between the Ru^III complexes and has a rare Icy-c* cubic network topology with a twofold interpenetration without crystal anisotropy. The crystals show a proton conductivity of 3.08×10⁻⁵ S cm⁻¹ at 450 K and a faster conductivity than those formed by only HIms. The high proton conductivity is attributed to not only molecular rotations and hopping motions of HIm frameworks that are activated at ∼113 K, but also isotropic whole-molecule rotation of [Ru^III(Him)₃(Im)₃] at temperatures greater than 420 K. The latter rotation was confirmed by solid-state ²H NMR spectroscopy; probable proton conduction routes were predicted and theoretically considered.     

A solid-supported acidic oxazolium perchlorate as an easy-handling catalyst for the synthesis of modified pyrimidine nucleosides via Vorbrüggen-type N-glycosylation

A solid-supported acidic oxazolium perchlorate was investigated as a heterogeneous catalyst in N-glycosylation reactions using silylated modified pyrimidines and an acylated ribose or glucose to afford the corresponding pyrimidine nucleosides. This salt is a nonhygroscopic and stable powder whose activity is comparable to that of 2-methyl-5-phenylbenzoxazolium perchlorate. A reaction with this polymer catalyst can be conducted on a gram scale. Reusability of the solid-supported catalyst was also investigated.     

Fluorescence properties of novel 6-butyl-2,3-dicyano-7-methyl-6H-1,4-diazepine styryl dyes containing ethyleneglycol units

The fluorescence properties of novel 6-butyl-2,3-dicyano-7-methyl-6H-1,4-diazepine styryl dyes having mono-, di-, tri-, and tetra(ethyleneglycol) units were examined. The mono(ethylenglycol) derivative was solid at room temperature, whereas the di-, tri-, and tetra(ethylenglycol) derivatives were oily. The monoethyleneglycol derivative showed weak aggregation-induced emission enhancement with fluorescence maximum at 649 nm, which comes from J-aggregates. The fluorescence of oily di-, tri-, and tetra(ethyleneglycol) derivatives in neat form was very weak. No aggregation-induced emission enhancement was observed for the oily derivatives.     

Synthesis of lipophilic bisanthracene fluorophores: versatile building blocks toward the synthesis of new light-harvesting dendrimers

Lipophilic bisanthracene-based fluorophore and its derivatives were synthesized by the Suzuki-Miyaura cross-coupling reaction of 9-anthrylboronic acid with a substituted dibromobenzene. In addition to desirable fluorescent properties, these molecular systems were demonstrated to serve as versatile building blocks toward the synthesis of two types of new light-harvesting dendrimers due to their chemical stability.     

Meeting announcement

Diffusion and solution behavior of methanol vapor in two diblock copolymers, poly(2-vinylpyridine)—block—polyisoprene [P(2VPbI)] and poly(2-vinylpyridine)—block—polystyrene [P(2VPbS)], was studied by the weighing method at 25°C. The domain structure of films of both copolymers showed an alternating lamellar arrangement. Methanol is a good solvent for P2VP, but a nonsolvent for PI and PS. Methanol dissolved exclusively in the P2VP phase of the copolymers. For both copolymer systems, absorption and desorption processes of non-Fickian type were observed as characterized by a thickness anomaly. However, the magnitude of the deviations from purely Fickian behavior was small, and the integral diffusion coefficient, D?, was obtainable with reasonable accuracy. At low and medium concentrations, D? for P(2VPbI) was greater, by about one order of magnitude, than that for P2VP, while D? for P(2VPbS) was lower than that for P2VP. A similar trend was observed in plots of the permeability coefficient against the vapor pressure of methanol. The results indicate that the rubbery PI phase may facilitate the transport of penetrant molecules in the P(2VPbI) film. On the other hand, the glassy PS phase in the P(2VPbS) film merely interferes with the transport of methanol molecules.     

A novel synthesis of α-methylene-γ-butyrolactones from 1-(N,N-dimethylaminomethyl)cyclopropanecarboxylate esters

A new method is reported for constructing α-methylene-γ-butyrolactone moiety under neutral, anhydrous conditions. Olefin-dibromocarbene adducts are transformed to methyl 1-(N,N-dimethylaminomethyl)cyclopropanecarboxylates which in turn are treated with trimethylsilyl iodide and the crude products distilled to give the title compounds with high regio- and stereoselectivity.