Solvent-Driven Association and Dissociation of the Hydrogen-Bonded Protonated Decavanadates
Solvent-Driven Association and Dissociation of the Hydrogen-Bonded Protonated Decavanadates
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DOI：
10.1021/ja110781f
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发表时间：
2011-05-18
影响因子：
15
通讯作者：
Ozeki, Tomoji
中科院分区：
文献类型：
--
作者：
Kojima, Tatsuhiro;Antonio, Mark R.;Ozeki, Tomoji
在丙酮和1，4-二氧六环混合溶剂中，用系统小角X射线散射和H-1、V-51核磁共振光谱研究了非水溶液中十钒酸根阴离子[HnV10O28]((6-n)-)在氢键辅助下的分子聚集。在富丙酮条件下，十钒阴离子倾向于自缔合氢键二聚体{[H3V10O28](2)}(6-)，随着1，4-二氧六环比例的增加，该二聚体分解为单体物种。十钒酸根阴离子的缔合/解离行为被证明是可逆的，并且是由溶剂的亲原疏水性质驱动的。
Hydrogen-bond-assisted molecular aggregation of decavanadate anions, [HnV10O28]((6-n)-), in nonaqueous solutions was probed by systematic small-angle X-ray scattering and H-1 and V-51 NMR spectroscopic measurements in mixtures of acetone and 1,4-dioxane. Under acetone-rich conditions, the decavanadate anion prefers a self-associated hydrogen-bonded dimer of {[H3V10O28](2)}(6-), which dissociates into monomeric species as the proportion of 1,4-dioxane increases. The association/dissociation behaviors of the decavanadate anions were proven to be reversible and driven by the protophobic/protophilic nature of the solvent.