权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

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.

二茂铁及其烷基衍生物和二茂铁烷基铵阳离子衍生物插层到VOP0_4层间形成VOPO_4·H_2O·（FcR）_x [Fc =（C_5H_5）Fe（C_5H_<4^->）; R = H，Me，Et和（CH_2）_nNR 'R”_2^+（n = 1，2 ; R'，R”= H，Me）; x = 0.17-0.45]。V（V）位点被二茂铁基（Fc）中心和作为二茂铁基烷基铵化合物的抗衡阴离子的I^-离子还原，导致Fc衍生物的包含。一些带有NH_3^+和NHMe_2^+基团的二茂铁烷基铵阳离子在层间空间中近似垂直于VOPO_4片层排列，这是由于这些铵基团可能靠近V（IV）位。另一方面，带有-NMe_3^+基团的二茂铁烷基铵阳离子不能接近V位，导致分子排列与VOPO_4片层平行。此外，靠近V（V）位点的Fc基团被氧化，形成Fc^+中心，而位于或多或少远离V位点的Fc基团以未氧化形式存在于层间空间中。V（IV）离子的ESR信号被位于V（IV）位置附近的顺磁性Fe ^+中心加宽，这是由快速自旋弛豫过程引起的。得到了几种以二茂铁烷基铵阳离子为客体分子的凝胶-V_2 O_5插层化合物。由于相邻的V-V距离较短，它们近似平行于以Fe（III）为中心的V_2O_5片排列。客体分子在VOPO_4和V_2O_5层间空间中的排列和电子态取决于V（IV）位与Fe中心和铵基的接近程度。