Detection of O(3P(J)) atoms formed by reaction, Al+O2--> AlO+O under crossed-beam condition

The vacuum ultraviolet laser-induced fluorescence technique was employed to detect the oxygen atoms formed by the reaction, Al+O(2)--> AlO+O. The measurements were carried out under the crossed-beam condition at 12.2 kJmol of collision energy. The relative populations of three spin-orbit states of O((3)P(J)) were determined to be 3.8, 1.0, and 0.2 for J=2, 1, and 0, respectively. They show nonstatistical populations, i.e., more population in O((3)P(2)) and less population in O((3)P(0)) than the statistical expectation. These populations were almost identical for two Al beam conditions where the relative concentrations of two spin-orbit states of Al, (2)P(1/2), and (2)P(3/2), are different. These results suggest that the reaction of Al with O(2) proceeds via an intermediate complex where the memory of the initial spin-orbit state is lost. Deviation from the statistical population of O((3)P(J)) implies the occurrence of the interaction among potential surfaces in the exit channel.     

Synthesis of A C18 alcohol from methyl oleate over hydrogen storage alloys

Catalytic hydrogenolysis of methyl oleate to C₁₈ alcohol is tested with a pulse reaction system under atomspheric pressure at 503 K over a series of hydrogen storage alloys. Mg₂Cu alloy shows the highest efficiency and the yield of alcohol is about three times larger than the classical Cu–Cr–O catalyst.

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-C₁₈ 503 K , . Mg₂Cu Cu–Cr–O.

     

Synthesis of 1-azacycl[3.2.2]azine and 1-azabenzo[h]cycl[3.2.2]azine

1-Azacycl[3.2.2]azines were synthesized from 2-methylthioimidazo[1,2-a]pyridines, 2a and 2b , by using [2 + 8] cycloaddition reaction with dimethyl acetylenedicarboxylate as the key step. Synthesis of 1-azabenzo-[h]cycl[3.2.2]azine was also described.     

The A-site ordered manganese perovskite and its colossal magnetoresistance

The A-site ordered manganites show the charge/orbital order (CO) transition far above room temperature. By using this advantage, we have engaged in the realization of colossal magnetoresistance (CMR) at room temperature by introducing some sophisticated disorders to SmBaMn₂O₆. The inter-site disorder of Sm/Ba results in no significant magnetoresistance (MR) effect. The La-substitution for both Sm- and Ba-sites is effective to realize MR effect. At room temperature and 9 T, we have achieved the record of MR effect about 340% in the sintered Sm_0.90La_0.24Ba_0.86Mn₂O₆. In a single crystal of the compound, the perfect CO insulator to ferromagnetic metal (FM) transition is observed at 9 T, showing the room temperature CMR over 1000%. TEM study reveals that the formation of microdomains with CO and FM or magnetic glassy states is crucial for CMR.     

Pulsed laser-induced oxygen deficiency at TiO2 surface: Anomalous structure and electrical transport properties

We have studied pulsed laser-induced oxygen deficiencies at rutile TiO₂ surfaces. The crystal surface was successfully reduced by excimer laser irradiation, and an oxygen-deficient TiO_2−δ layer with 160 nm thickness was formed by means of ArF laser irradiation at 140 mJ/cm² for 2000 pulses. The TiO_2−δ layer fundamentally maintained a rutile structure, though this structure was distorted by many stacking faults caused by the large oxygen deficiency. The electrical resistivity of the obtained TiO_2−δ layer exhibited unconventional metallic behavior with hysteresis. A metal–insulator transition occurred at 42 K, and the electrical resistivity exceeded 10⁴ Ω cm below 42 K. This metal–insulator transition could be caused by bipolaronic ordering derived from Ti–Ti pairings that formed along the stacking faults. The constant magnetization behavior observed below 42 K is consistent with the bipolaronic scenario that has been observed previously for Ti₄O₇. These peculiar electrical properties are strongly linked to the oxygen-deficient crystal structure, which contains many stacking faults formed by instantaneous heating during excimer laser irradiation.     

Rubidium metavanadate formation at room temperature under vacuum ultraviolet irradiation from metal-organic compositions

White light emitting phosphor RbVO₃ films have been successfully fabricated by means of a vacuum ultraviolet (VUV) irradiation using an excimer lamp after spin coating of metal-organic solution onto substrates. The metal-organic carboxylates coated on substrates decomposed and reacted under the VUV irradiation. The metal-organic bonds were efficiently cleaved by the VUV illumination not only in air but also in vacuum, however, there was not a strong driving force for the reaction process to the formation of RbVO₃ in the vacuum atmosphere. On the contrary, the reaction and crystallization simultaneously proceeded under photo-chemically produced active oxygen and/or ozone atmospheres due to the VUV illumination in air. The reaction between the photo-activated Rb-O and V-O species could be strongly enhanced by the oxidation atmospheres at the moment of the metal-organic bond cleavage under the VUV irradiation.     

Anthracene‐Attached Persistent Tricyclic Aromatic Hydrocarbon Radicals

Anthracene‐attached tricyclic aromatic hydrocarbon radicals having different central polygons, Ant‐5 , Ant‐6 , and Ant‐7 , were synthesized to evaluate the role of an anthracene substituent group in the stability and reactivity of tricyclic aromatic hydrocarbon radicals. The bulky anthryl group effectively protects a carbon atom with high spin density, resulting in high persistence of the radicals. On the other hand, the combination of the anthryl group and the tricyclic aromatic scaffold makes the molecular structure drastically change from a twisted form to a folded form and an unpaired electron moves into the anthryl moiety, eventually affording a tail‐to‐tail σ‐dimer.     

Chemoselective Catalytic Asymmetric Synthesis of Functionalized Aminals Through the Umpolung Organocascade Reaction of α‐Imino Amides

Chiral functionalized aminals are important core structures of natural products and pharmaceuticals. Their chemo‐ and regioselective catalytic, asymmetric synthesis has been realized through the umpolung reaction of α‐imino amides using a catalyst we originally developed. Functionalized aminals were prepared with high chemoselectivity by treating a hemiaminal intermediate with pyridine in butanol. Evaluation of substrate scope revealed that this transformation could be achieved with a wide range of α‐imino amides to produce the desired products in high yields with up to 97 % ee. A mechanistic study suggested that aminal formation proceeded through the ring opening/ring closing equilibrium of the hemiaminal skeleton.     

Discovery and development of microporous metal carboxylates

We have found a form of copper(II) terephthalate that occluded an enormous amount of gases such as N2, Ar, O2, and Xe. Copper(II) terephthalate is the first metal complex found capable of adsorbing gases. This complex has opened a new field of adsorbent chemistry and is recognized as a leader in the construction of microporous metal complexes. In extending the route for the synthesis of microporous complexes, we obtained many new porous materials that are widely recognized as useful materials for applications in areas such as gas storage, molecular sieves, catalysis, inclusion complexes, and surface science.