Solvation and inclusion of rare earth elements in gas phase

气相中稀土元素的溶解和包合

基本信息

批准号：
10640498
负责人：
YAMADA Yasuhiro
金额：
$ 1.98万
依托单位：
Science University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 1999
项目状态：
已结题

项目摘要

Rare earth elements and their compound in gas phase are studied in order to obtain the information of their solvation and bonding natures. In this study, photochemistry of lanthanide complexes isolated in low-temperature matrices and gas-phase cluster ions produced by supersonic expansion were studied. Photoreduction of matrix-isolated tetrakis(acetylacetonato)cerium(IV) produced tris(acetylacetonato)cerium(III) and acetylacetone radical. The acetylacetone radical produced keto-form acetylaceton by the subsequent reactions, whereas enol-form is known to be stable in normal condition. The matrix-isolated tris(cyclopentadienyl)neodymium was found to have a structure different from that of solid compounds (polymer structures). The small polymer with bridged cyclopentadiene and the monomer compounds are formed in matrices depending on the concentration. The monomer species isolated in low-temperature matrices species isolated in low-temperature matrices was found to have three σ -bonded cycropentadiene. Solvent clusters in gas-phase were produced by supersonic expansion, and their mass spectra were observed in order to study the solvation mechanism. The gas phase clusters may provide a simple model of solution system. Mixed clusters of dioxane and water molecules were studied as they form the hydrogen-bonded network structures. The cluster with three 1, 4-dioxane molecules connected to oxonium ion was found to be the stable cluster ion, and a pair of one dioxane and one water molecule attachs to form larger clusters with hydrogen bonds.

研究气相中的稀土元素及其化合物，以获得其溶剂化和成键性质的信息。本研究研究了低温基质中分离的稀土配合物和超声膨胀产生的气相簇离子的光化学。基质分离的四（乙酰丙酮）铈（IV）的光还原产生三（乙酰丙酮）铈（III）和乙酰丙酮自由基。乙酰丙酮自由基通过后续反应产生酮形式的乙酰丙酮，而已知烯醇形式在正常条件下是稳定的。发现基质分离的三(环戊二烯基)钕具有与固体化合物(聚合物结构)不同的结构。具有桥联环戊二烯的小聚合物和单体化合物根据在低温基质中分离的浓度而在基质中形成。通过超音速膨胀，发现低温基质中存在三个σ键合的环戊二烯，并观察了它们的质谱，为研究气相簇提供了一个简单的模型。研究了二恶烷和水分子的混合簇形成氢键网络结构，该簇具有三个与氧鎓离子连接的1, 4-二恶烷分子。被发现是稳定的簇离子，一对二恶烷和一个水分子通过氢键连接形成更大的簇。