Li, Z.*; Piankova, D.*; Yang, Y.*; Kumagai, Yuta; Zschiesche, H.*; Jonsson, M.*; Tarakina, N. V.*; Soroka, I. L.*
Angewandte Chemie; International Edition, 61(6), p.e202112204_1 - e202112204_9, 2022/02
The role of intermediate phases in CeO mesocrystal formation from aqueous Ce(III) solutions subjected to -radiation was studied. Radiolytically formed hydroxyl radicals convert soluble Ce(III) into less soluble Ce(IV). Transmission electron microscopy and X-ray diffraction studies of samples from different stages of the process allowed the identification of several stages in CeO mesocrystal evolution following the oxidation to Ce(IV): (1) formation of hydrated Ce(IV)-hydroxides, serving as intermediates in the liquid-to-solid phase transformation; (2) CeO primary particle growth inside the intermediate phase; (3) alignment of the primary particles into "pre-mesocrystals" and subsequently to mesocrystals, guided by confinement of the amorphous intermediate phase and accompanied by the formation of mineral bridges. Further alignment of the obtained mesocrystals into supracrystals occurs upon slow drying, making it possible to form complex hierarchical architectures.
Chiera, N. M.*; Sato, Tetsuya; Eichler, R.*; Tomitsuka, Tomohiro; Asai, Masato; Adachi, Sadia*; Dressler, R.*; Hirose, Kentaro; Inoue, Hiroki*; Ito, Yuta; et al.
Angewandte Chemie; International Edition, 60(33), p.17871 - 17874, 2021/08
The formation and the chemical characterization of single atoms of dubnium (Db, element 105), in the form of its volatile oxychloride, was investigated using the on-line gas phase chromatography technique, in the temperature range 350 - 600 C. Under the exact same chemical conditions, comparative studies with the lighter homologs of group-5 in the Periodic Table clearly indicate the volatility sequence being NbOCl TaOCl DbOCl. From the obtained experimental results, thermochemical data for DbOCl were derived. The present study delivers reliable experimental information for theoretical calculations on the chemical properties of transactinides.
Lai, W.-H.*; Wang, H.*; Zheng, L.*; Jiang, Q.*; Yan, Z.-C.*; Wang, L.*; Yoshikawa, Hirofumi*; Matsumura, Daiju; Sun, Q.*; Wang, Y.-X.*; et al.
Angewandte Chemie; International Edition, 59(49), p.22171 - 22178, 2020/12
Wang, Y.*; Dong, X.*; Tang, X.*; Zheng, H.*; Li, K.*; Lin, X.*; Fang, L.*; Sun, G.*; Chen, X.*; Xie, L.*; et al.
Angewandte Chemie; International Edition, 58(5), p.1468 - 1473, 2019/01
Pressure-induced polymerization (PIP) of aromatics is a novel method to construct sp-carbon frameworks, and nanothreads with diamond-like structures were synthesized by compressing benzene and its derivatives. Here by compressing benzene-hexafluorobenzene cocrystal(CHCF), we identified H-F-substituted graphane with a layered structure in the PIP product. Based on the crystal structure determined from the in situ neutron diffraction and the intermediate products identified by the gas chromatography-mass spectrum, we found that at 20 GPa CHCF forms tilted columns with benzene and hexafluorobenzene stacked alternatively, which leads to a [4+2] polymer, and then transfers to short-range ordered hydrogenated-fluorinated graphane. The reaction process contains [4+2] Diels-Alder, retro-Diels-Alder, and 1-1' coupling, and the former is the key reaction in the PIP. Our studies confirmed the elemental reactions of the CHCF for the first time, which provides a novel insight into the PIP of aromatics.
Lang, R.*; Li, T.*; Matsumura, Daiju; Miao, S.*; Ren, Y.*; Cui, Y.-T.*; Tan, Y.*; Qiao, B.*; Li, L.*; Wang, A.*; et al.
Angewandte Chemie; International Edition, 55(52), p.16054 - 16058, 2016/12
Takagi, Shigeyuki*; Iijima, Yuki*; Sato, Toyoto*; Saito, Hiroyuki; Ikeda, Kazutaka*; Otomo, Toshiya*; Miwa, Kazutoshi*; Ikeshoji, Tamio*; Aoki, Katsutoshi*; Orimo, Shinichi*
Angewandte Chemie; International Edition, 54(19), p.5650 - 5653, 2015/05
Ribas-Arino, J.*; Shiga, Motoyuki; Marx, D.*
Angewandte Chemie; International Edition, 48(23), p.4190 - 4193, 2009/04
To control the chemical bond breaking by mechanical forces is a newly growing field called "mechanochemistry", but theoretical background has not been established. Here we suggest a new approach to apply Fukui's intrinsic reaction coordinate concept to molecular motion on adiabatic potential surface distorted by external force. Using this approach we explain the mechanism of forbidden pericyclic reaction in recent ultrasound experiment.
Tanaka, Hirohisa*; Taniguchi, Masashi*; Uenishi, Mari*; Kajita, Nobuhiko*; Tan, Isao*; Nishihata, Yasuo; Mizuki, Junichiro; Narita, Keiichi*; Kimura, Mareo*; Kaneko, Kimiyoshi*
Angewandte Chemie; International Edition, 45(36), p.5998 - 6002, 2006/09
no abstracts in English