Influences of Acid on Molecular Forms of Fluorescein and Photoinduced Electron Transfer in Fluorescein‐Dispersing Sol–Gel Titania Films

Fluorescein‐dispersing titania gel films were prepared by the acid‐catalyzed sol–gel reaction using a titanium alkoxide solution containing fluorescein. The molecular forms of fluorescein in the films, depending on its acid–base equilibria, and the complex formation and photoinduced electron transfer process between the dye and titania surface were investigated by fluorescence and photoelectric measurements. The titanium species were coordinated to the carboxylate and phenolate‐like groups of the fluorescein species. The quantum efficiencies of the fluorescence quenching and photoelectric conversion were higher upon excitation of the dianion species interacting with the titania, i.e. the dye–titania complex. This result indicated that the dianion form was the most favorable for formation of the dye–titania complex exhibiting the highest electron transfer efficiency. Using nitric acid as the catalyst, the titania surface bonded to the fluorescein instead of the adsorbed nitrate ion during the steam treatment. The dye–titania complex formation played an important role in the electron injection from the dye to the titania conduction band.     

Catalytic Activity of Molybdenum Complexes Bearing PNP-Type Pincer Ligand toward Ammonia Formation

We newly designed and prepared a novel molybdenum complex bearing a 4-[3,5-bis(trifluoromethyl)phenyl]pyridine-based PNP-type pincer ligand, based on the bond dissociation free energies (BDFEs) of the N−H bonds in molybdenum-imide complexes bearing various substituted pyridine-based PNP-type pincer ligands. The complex worked as an excellent catalyst toward ammonia formation from the reaction of an atmospheric pressure of dinitrogen with samarium diiodide as a reductant and water as a proton source under ambient reaction conditions, where up to 3580 equivalents of ammonia were formed based on the molybdenum atom of the catalyst. The catalytic activity was significantly improved by one order of magnitude larger than that observed when using the complex before modification.     

Synergic Catalysis of PdCu Alloy Nanoparticles within a Macroreticular Basic Resin for Hydrogen Production from Formic Acid

Highly dispersed PdCu alloy nanoparticles have been successfully prepared within a macroreticular basic resin bearing ?N(CH₃)₂ functional groups. This previously unappreciated combination of alloy is first proven to be responsible for the efficient production of high‐purity H₂ from formic acid (HCOOH) dehydrogenation for chemical hydrogen storage. By the addition of Cu, the electronically promoted Pd sites show significantly higher catalytic activity as well as a better tolerance towards CO poisoning as compared to their monometallic Pd counterparts. Experimental and DFT calculation studies revealed not only the synergic alloying effect but also cooperative action by the ?N(CH₃)₂ groups within the resin play crucial roles in achieving exceptional catalytic performances. In addition to the advantages such as, facile preparation method, free of additives, recyclable without leaching of active component, and suppression of unfavorable CO formation less than 3 ppm, the present catalytic system is cost‐effective because of the superior catalytic activity compared with that of well‐established precious PdAg or PdAu catalysts. The present catalytic system is particularly desirable for an ideal hydrogen vector in terms of potential industrial application for fuel cells.     

Synthetic study of biphenylquinolizidine alkaloids I. Asymmetric total synthesis of lasubine I featuring organocatalyzed asymmetric intramolecular aza-Michael addition

A new procedure for the asymmetric total synthesis of lythraceous alkaloids with a 4-arylquinolizidine skeleton was developed, which involved an organocatalyzed asymmetric intramolecular aza-Michael addition.     

Torreyanoxane,a New 3,4‐Secoglutinane Triterpenoid Isolated from the Pulp of Torreya nucifera

Torreyanoxane, a novel 3,4‐secoglutinane triterpenoid, was isolated from the pulp of Torreya nucifera. The structure was determined on the basis of spectroscopic methods.     

Induced Fitting and Polarization of a Bromine Molecule in an Electrophilic Inorganic Molecular Cavity and Its Bromination Reactivity

Dodecavanadate, [V₁₂O₃₂]^4? (V12), possesses a 4.4 Å cavity entrance, and the cavity shows unique electrophilicity. Owing to the high polarizability, Br₂ was inserted into V12, inducing the inversion of one of the VO₅ square pyramids to form [V₁₂O₃₂(Br₂)]^4? (V12(Br2)). The inserted Br₂ molecule was polarized and showed a peak at 185 cm^?1 in the IR spectrum. The reaction of V12(Br2) and toluene yielded bromination of toluene at the ring, showing the electrophilicity of the inserted Br₂ molecule. Compound V12(Br2) also reacted with propane, n‐butane, and n‐pentane to give brominated alkanes. Bromination with V12(Br2) showed high selectivity for 3‐bromopentane (64 %) among the monobromopentane products and preferred threo isomer among 2‐,3‐dibromobutane and 2,3‐dibromopenane. The unique inorganic cavity traps Br₂ leading the polarization of the diatomic molecule. Owing to its new reaction field, the trapped Br₂ shows selective functionalization of alkanes.