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Pure Appl. Chem., 2009, Vol. 81, No. 7, pp. 1323-1330

Published online 2009-06-29

Synthesis of a bowl-type dodecavanadate by the coupling reaction of alkoxohexavanadate and discovery of a chiral octadecavanadate

Kyosuke Domae1, Daisuke Uchimura1, Yuuki Koyama1, Shinnosuke Inami1, Yoshihito Hayashi1*, Kiyoshi Isobe1, Hiroyuki Kameda2 and Tatsuya Shimoda2,3

1 Department of Chemistry, Graduate School of Natural Science, Kanazawa University, Kakuma, Kanazawa, 920-1192, Japan
2 JST, ERATO, Shimoda Nanoliquid Process Project, 2-5-3 Asahidai, Nomi-shi, Ishikawa 923-1211, Japan
3 School of Materials Science, Japan Advanced Institute of Science and Technology (JAIST), 1-1 Asahidai, Nomi, Ishikawa 923-1292, Japan

Abstract: A new route to an alkoxohexavanadate species leads to the isolation of a bowl-type dodecavanadate without a guest molecule in the cavity. The 1D tetravanadate, [V4O11]2-, is a good precursor for the alkoxohexavanadate, [V6O13(OCH3)6]2-, which is then utilized for the [V6 + V6] coupling reaction to form the dodecavanadate, [V12O42]4-, with a capped dichloromethane molecule at the cavity entrance. We also obtained structural information on a newly discovered octadecavanadate,  [V18O46(NO3)]5-,in both the solid and solution states through extended X-ray absorption fine structure (EXAFS) studies. The existence of a chiral inorganic species in acetonitrile with double-stranded V8 chains was confirmed through EXAFS oscillations.