半球状ポリオキソバナデートのホストゲスト化学とその骨格変換

13301甲第4723号博士（理学）金沢大学博士論文本文Ful

半球状ポリオキソバナデートのホストゲスト化学とその骨格変換

13301甲第4723号博士（理学）金沢大学博士論文要旨Abstrac

A chloride capturing system: Via proton-induced structure transformation between opened- and closed-forms of dodecavanadates

Chloride-incorporated dodecavanadates show two distinct structures of the monoprotonated-form [HV12O32(Cl)]4- (closed-V12) with a spherical closed-structure and the opened-form [V12O32(Cl)]5- (opened-V12). The reaction of closed-V12 with a stoichiometric amount of ethylenediamine drives the structure transformation reaction to opened-V12, quantitatively. From time dependent observations of 51V NMR, a tube-type intermediate [V12O32(Cl)]5- (tube-V12) was observed in the transformation process. Isolation of the intermediate was achieved by the deprotonation reaction of closed-V12 with diethylamine, and the structure transformation was confirmed by using the isolated intermediate. The reverse transformation from opened-V12 to closed-V12 was also achieved by addition of trifluoroacetic acid. The geometrical difference between closed-V12 and opened-V12 is reflected in the reactivity difference to the external reagents, and this was demonstrated by examining the chloride removal reaction by using a silver cation. The incorporated chloride was preserved in the closed-V12 cage even in the presence of a silver cation. In contrast, the chloride in opened-V12 was removed as AgCl by the silver cation. In addition, by the reaction of chloride-free opened-V12 with a quantitative amount of {Et4N}Cl retrieved opened-V12, showing the capability of opened-V12 to recapture a guest chloride in the cavity. This transformation between two isomeric dodecavanadate structures is regarded as the movement of a molecular mitt to catch a ball and secure it. © 2016 The Royal Society of Chemistry.Embargo Period 12 month

Structural conversion from bowl- to ball-type polyoxovanadates: Synthesis of a spherical tetradecavanadate through a chloride-incorporated bowl-type dodecavanadate

A spherical tetradecavanadate, [V14O38(Cl)] 7-, was synthesized from a chloride-incorporated bowl-type dodecavanadate. © 2014 Elsevier B.V. All rights reserved