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

我们将有机、有机金属分子和金属络合物插入到无机化合物的层间空间中，研究了层间空间中客体分子的分子排列和电子态，发现了它们独特的物理性质和反应活性。1)二茂铁衍生物插入混合钒-铌磷酸盐的层间空间，客体分子在空间中的行为阐明了它们在氧化还原反应形成的VOPO_4层间化合物中的排列和电子态的基本特征。2)3-甲基和3.5-二甲基吡咯插入到VOPO_4层间空间，伴随着聚合反应来买得起插层化合物。4-苯胺也在VOPO_4和V_2O_5的夹层空间中聚合，并阐明了聚合过程。3)取代喹啉和异构体…在α-磷酸锆层间插入了更多的Inoline阳离子和acridine阳离子。测量了它们的荧光光谱和荧光寿命。与在溶液中相比，层间空间的寿命有所缩短，并且存在寿命较短的组分，寿命为4-5 ns。4)几种取代的吡啶类化合物和联吡啶化合物被插入到V_2O_5层间空间，其中的吡啶氮原子被部分质子化。质子化氮原子的丰度不取决于客体分子的碱性强度。质子化受层间水分子离解引起的电荷分离的影响。层间距离随着主体层中每钒质子化氮原子丰度的增加而增加。5)合成了含自旋交叉铁(II或II)络合物的NaTMS粘土插层化合物。ESR谱和它们的磁化率随温度的变化表明，这些金属络合物在粘土夹层空间中有两个或三个环境，在较宽的温度范围内发生了高自旋态和低自旋态之间的变化。估算了自旋态平衡的热力学参数。较少

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