Study on New VOPO_4-Intercalation Compounds with Metal- and Organometallic Complexes

新型VOPO_4-金属和有机金属配合物插层化合物的研究

基本信息

批准号：
02640477
负责人：
MATSUBAYASHI Gen-etsu
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：
1990
资助国家：
日本
起止时间：
1990 至 1991
项目状态：
已结题

项目摘要

Ferrocene, its alkyl derivatives, and ferrocenylalkylammonium cation derivatives have been intercalated into the VOP0_4 interlayer to form the intercalation compounds ; VOPO_4・H_2O・(FcR)_x [Fc = (C_5H_5)Fe(C_5H_<4^->) ; R = H, Me, Et and (CH_2)_nNR'R"_2^+ (n = 1, 2 ; R', R" = H, Me) ; x = 0.17-0.45]. The V(V) site is reduced by the ferrocenyl (Fc) center and the I^- ion as the counter anion of the ferrocenylalkylammonium compounds, resulting in the inclusion of the Fcderivatives. Some ferrocenylalkylammonium cations with the NH_3^+ and NHMe_2^+ groups are arranged approximately perpendicular to the VOPO_4 sheet in the interlayer space owing to the possible proximity of these ammonium groups to the V(IV) site. On the other hand, the ferrocenylalkylammonium cations with the -NMe_3^+ group cannot approach the V site, leading to the arrangement of the molecule parallel to the VOPO_4 sheet. Furthermore, the Fc group in the proximity to the V(V) site is oxidized leading to the Fc^+ center, while the Fc group located more or less remote from the V site exists in the unoxidized form in the interlayer space. The ESR signal of the V(IV) ion is broadened by the paramagnetic Fc^+ center located in the proximity of the V(IV) site, which is caused by the rapid spin-relaxation process. Several intercalation compounds of gel-V_2O_5 with the guest molecules of the ferrocenylalkylammonium cations have been obtained. They are arranged approximately parallel to the V_2O_5 sheet with the Fe(III) center, which is due to the rather short adjacent V-V distance. Molecular arrangements and electronic states of the guest molecules in the VOPO_4 and V_2O_5 interlayer spaces are concluded to be determined by the extent of the proximity of the V(IV) site to the Fc center and the ammonium groups.

二革新，其烷基衍生物和亚丙基烯基氨基氨基阳离子衍生物已被插入VOP0_4中间层中，形成了相互量化的化合物。 vopo_4 ・ h_2o ・（fcr）_x [fc =（c_5h_5）fe（c_5h_ <4^ - >）; r = h，我，et and（ch_2）_nnr'r“ _2^+（n = 1，2; r'，r'，r” = h，me）; x = 0.17-0.45]。 V（v）位点通过甲氧基（FC）中心和I^离子降低，作为甲基丙基烷基铵化合物的反式阴离子，从而纳入了fcdedrivatives。由于这些氨基组可能接近V（iv（iv））位点，因此一些具有NH_3^+和NHME_2^+基的甲基苯基氨基氨基阳离子与NHME_2^+基团在层间空间中的VOPO_4板近似垂直。另一方面，带有-nme_3^+组的铁丙基烷基氨基阳离子无法接近V位点，从而导致平行于VOPO_4纸的分子排列。此外，靠近V（V）位点的FC组被氧化导致FC^+中心，而FC组或多或少远离V站点的FC组以层间空间中的未氧化形式存在。 V（iv）离子的ESR信号通过位于V（IV）位点的接近度中的顺磁FC^+中心扩大，该中心是由快速自旋 - 浮肿过程引起的。已经获得了凝胶V_2O_5的几种插入化合物与甲基苯基烷基氨基阳离子的宾客分子。它们与Fe（III）中心的V_2O_5板大致排列，这是由于相当短的相邻V-V距离所致。 VOPO_4和V_2O_5中间层间空间中客人分子的分子排列和电子状态得出的结论是由V（IV）位点与FC中心和氨基组的接近程度确定的。