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Arrangements, Reactivities and Functions of Organic and Organometallic Molecules in Inorganic Layred Spaces

无机层状空间中有机和有机金属分子的排列、反应性和功能

基本信息

批准号：
06640721
负责人：
MATSUBAYASHI Genetsu
金额：
$ 1.28万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1995
项目状态：
已结题

项目摘要

We have intercalated organic, organometallic molecules and metal complexes into the interlayr spaces of inorganic compounds and studied molecular arrangements and electronic states of guest molecules in the interlayr spaces and found unique physical properties and reactivities of them characteristic of those in the interlayr spaces.1) Intercalation of ferrocenyl derivatives into the interlayr spaces of mixed vanadyl-niobyl phosphates and behaviors of the guest molecules in the spaces have clarified the fundamental characteristics of them in arrangements and electronic states in the interlayr space of the VOPO_4-intercalation compounds formed by redox reactions.2) 3-Methyl-and 3.5-dimethylpyrrole have been intercalated into the VOPO_4 interlayr space, accompanied with polymerization, to afford intercalation compounds. 4-Anilinoaniline has been also polymerized in the VOPO_4 and V_2O_5 interlayr spaces and the polymerization process has been clarified.3) Substituted quinolinium and isoqu … More inolinium cations and the acridinium cation have been intercalated into the interlayr space alpha-zirconium phoshate. Fluorescence spectra and fluorescence lifetimes of them have been measured. The lifetimes are somewhat shortened in the interlayr space compared with in solution, and components having short lifetimes of 4-5 ns are present in the interlayr space.4) Several substituted pyridine derivatives and dipyridyl compounds have been intercalated into the V_2O_5 interlayr space, where pyridyl nitrogen atoms have been partially protonated. The abundances of the protonated nitrogen atoms do not depend on strengths of basicity of a guest molecule. Protonation is affected by the charge separation due to dissociation of water molecules in the interlayr space. The interlayr distances have been clarified to be lengthened with the increase of the abundances of protonated nitrogen atoms per vanadium of the host layr.5) NaTMS clay-intercalation compounds containing spin-crossover iron (II or II) complexes have been prepared. ESR spectra and temperature-dependence of magnetic susceptibilities of them have clarified that these metal complexes have two or three surroundings in the clay interlayr space, the changes between high spin and low spin states occurring in the wide temperature range. Thermodynamic parameters of the equilibria in the spin states have been estimated. Less

我们把有机物，将有机金属分子和金属配合物插入无机化合物的层间空间，研究了客体分子在层间空间的分子排列和电子状态，发现了客体分子在层间空间的独特物理性质和反应活性。3）3-甲基吡咯和3.5-二甲基吡咯分别插层到VOPO_4层间，形成了VOPO_4插层化合物，并对VOPO_4插层化合物的结构和性质进行了研究4层间距，并伴随聚合反应，以提供插层化合物。4-苯胺基苯胺在VOPO_4和V_2O_5层间也发生了聚合，并阐明了聚合过程 ...更多信息吲哚鎓阳离子和吖啶鎓阳离子已经插入层间空间α-磷酸锆中。测量了它们的荧光光谱和荧光寿命。在V_2O_5的层间空间中，吡啶氮原子被部分质子化，取代吡啶衍生物和联吡啶化合物被插入到V_2O_5的层间空间中。质子化氮原子的丰度不依赖于客体分子的碱性强度。质子化受到由于层间空间中的水分子解离而引起的电荷分离的影响。5）制备了含有自旋交叉铁（II或II）配合物的NaTMS粘土插层化合物。ESR谱和磁化率随温度的变化表明，这些金属配合物在粘土层间空间有两个或三个环境，在很宽的温度范围内发生高自旋态和低自旋态的转变。在自旋态平衡的热力学参数进行了估计。少