Highly Mesoporous Metal‐Organic Frameworks as Synergistic Multimodal Catalytic Platforms for Divergent Cascade Reactions

Rational engineering and assimilation of diverse chemo‐ and biocatalytic functionalities in a single nanostructure is highly desired for efficient multistep chemical reactions but has so far remained elusive. Here, we design and synthesize multimodal catalytic nanoreactors (MCNRs) based on a mesoporous metal‐organic framework (MOF). The MCNRs consist of customizable metal nanocrystals and stably anchored enzymes in the mesopores, as well as coordinatively unsaturated cationic metal MOF nodes, all within a single nanoreactor space. The highly intimate and diverse catalytic mesoporous microenvironments and facile accessibility to the active site in the MCNR enables the cooperative and synergistic participation from different chemo‐ and biocatalytic components. This was shown by one‐pot multistep cascade reactions involving a heterogeneous catalytic nitroaldol reaction followed by a [Pd/lipase]‐catalyzed chemoenzymatic dynamic kinetic resolution to yield optically pure (>99 % ee) nitroalcohol derivatives in quantitative yields.     

Steric effects upon transition states of radical addition polymerizations

Transition states (TSs) of radical addition homopolymerization reactions of methyl acrylate, methyl methacrylate, dimethyl itaconate, and N-methyl itaconimide were examined with two-unit radical models using MOPAC (PM3 UHF) semiempirical method. Calculated activation energies (E_as) show good correlations with experimental values. Calculated activation entropies (−ΔS^‡s) are found to be well proportional to E_as. The entropy terms play an important role as well as E_a in radical additions. E_a depends on the angle (θ_rs) between reaction points of radical and of monomer at TS. The bond length between reaction points at TS is constant regardless of monomers studied. The geometries and thermodynamical properties calculated here for TS indicate the importance of steric effects caused by substituted group(s) rather than electronic perturbation energies reported previously. © 1996 John Wiley & Sons, Inc.     

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.