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

铁氧烯、其烷基衍生物和铁氧烷胺转化衍生物已被插入VOP0_4中间层形成中间化合物; 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]。V（V）站点被ferrocenyl （Fc）中心和I^-离子减少为ferrocenylalkylammonium化合物的反离子，结果在Fcderivatives的包含中。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。在另一手上，铁氧基烷基氨酰胺与-NMe_3 ^+组无法接近V站点，将分子并行排列到VOPO_4表格上。Furthermore，在V（V）站点中的Fc组被氧化化引导到Fc^+中心，同时Fc组将更多或更少地从V站点存在于隔层空间中未氧化化的形式中。V（IV）离子的ESR信号被超磁性Fc^+位于V（IV）站点的中心，因为它是由快速旋转放松过程引起的。凝胶-V_2 O_5的几种相互作用化合物与铁氧基烷基铵的来宾分子已经被发现。他们用Fe（III）中心安排了一个近似平行的V_2O_5表格，它是相对于较短的V-V距离的。VOPO_4和V_2O_5中间层空间中来宾分子的分子安排和电子状态由V（IV）站点确定，以确定FC中心和氨组的近距离范围。

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.