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

Domae, Kyosuke; Uchimura, Daisuke; Koyama, Yuuki; Inami, Shinnosuke; Hayashi, Yoshihito; Isobe, Kiyoshi; Kameda, Hiroyuki; Shimoda, Tatsuya

doi:10.1351/PAC-CON-08-08-25

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

http://dx.doi.org/10.1351/PAC-CON-08-08-25

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 Shimoda^2,3

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.