Study on synthesis, structure and physical properties of metal endohedral C_<60>, and its development to new materials

金属内嵌C_<60>的合成、结构、物理性能研究及其新材料开发

• 批准号: 11165227
• 负责人: KUBOZONO Yoshihiro
• 金额: $ 10.5万
• 依托单位: Okayama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas (A)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11165227/
• 关键词: M@C_<60>; XANES; EXAFS; structure; electoronic state; superconductivity; physical property; 金属内包C60; 原子価; XAFS; 吸収スペクトル; 錯形成; 電子移動

Purified samples of metal endohedral C_<60> (M@C_<60>) have been prepared through the present project, and their structure and physical properties have been studied by XANES, EXAFS, Raman, UV-VIS-Near IR absorption, ESR and static susceptibility measurements. Large amounts of soots containing Eu@C_<60> and Dy@C_<60> were synthesized by arc-heating of metal oxide / graphite composite rods. The soot of Eu@C_<60> was sublimed at 450℃ under 10^<-6> Torr in order to eliminate Eu endohedral higher fullerenes, and the sublimate obtained was dissolved into a distilled aniline by a supersonic irradiation. On the other hand, the soot of Dy@C_<60> was directly dissolved into the distilled aniline. After repeating high performance liquid chromatography (HPLC) five times, the fraction exhibiting a single peak in the HPLC profile was collected, and the sample quality was checked by TOF-mass spectrum. The purity of Eu@C_<60> and Dy@C_<60> samples was 〜 99 %. The XANES of Eu@C_<60> and Dy@C_<60> showed that the valences of Eu and Dy were +2 and +3, respectively. The valences are accordance with those of Eu@C_<82> and Dy@C_<82>. The distance between Dy and the first nearest C atoms (Dy-C(1), and that between the Dy and the second nearest C atoms (Dy-C(2)) were determined to be 2.39(1) and 2.67(3) Å, respectively, on the basis of Dy L_<III>-edge EXAFS. The results show that the Dy atom lies on five-membered ring inside C_<60> cage ; the Dy is located at the off-center position by 1.25 Å. The Ag(2) Raman peak of Dy@C_<60> was observed at 1450 cm^<-1>. This shows that three electrons transfer from the Dy to the C_<60> cage. The ESR of Dy@C_<60> exhibited the g-factor of 2.0050 and line width of 4.5 G at 298 K. The ESR of Dy^<3+> was observed at 4.0 K, which implies that the spin of C_<60> appears by three-electrons transfer from Dy atom. The study on structure and physical properties of M@C_<60>・carbon nanotube hybrid materials in nanometer scale is now in progress.

金属内膜C_ <60>的纯化样品已经通过本项目制备，其结构和物理特性已经由Xanes，Exafs，Raman，UV-VIS-NEAR IR抽象，ESR，ESR和静态易感性测量进行了研究。通过金属氧化物 /石墨复合杆的弧加热，合成了大量包含EU@C_ <60>和DY@C_ <60>的烟灰。 EU@C_ <60>的烟灰在10^<-6>托尔的下面升华为450，以消除欧盟内膜高富勒烯，并通过超音速辐照将获得的升华的升华液溶解在蒸馏的苯胺中。另一方面，Dy@C_ <60>的烟灰直接溶解在蒸馏型苯胺中。在重复高性能液相色谱（HPLC）五次之后，收集了在HPLC剖面中进行单个峰的分数，并通过TOF-MAS频谱检查了样品质量。 EU@C_ <60>和DY@C_ <60>样本的纯度〜99％。 EU@C_ <60>和DY@C_ <60>的Xanes表明，欧盟和DY的价值分别为+2和+3。该价值与eu@c_ <82>和dy@c_ <82>的价值有关。 DY与第一个最近的CAR原子（DY-C（1）以及DY和第二个最近的CAR原子（DY-C（2））之间的距离分别为2.39（1）和2.67（1）和2.67（3）Å，根据Dy L_ <iii> - edge的基础，根据dy l_ <iii> - edges。结果表明，结果表明，dy atom在五个成员的位置上置于C _ 60> 1. offer coge的位置。 Å。 C_ <60>通过Dy Atom的三电子转移出现。

项目成果

宇留賀朋哉・・・久保園芳博・・・(著者18名中9番目): "The XAFS Beamline at Spring-8"Journal of Synchrotron Radiation. 6. 143-145 (1999)

Tomoya Uruga...Yoshihiro Kubozono...（18 位作者中的第 9 位）：“Spring-8 的 XAFS 光束线”同步辐射杂志 6. 143-145 (1999)。

久保園芳博・高林康裕 他5名: "Metal-Insulator transition at 50 K in Na_2C_<60>"Physical Review. B59(23). 15062-15069 (1999)

Yoshihiro Kubozono、Yasuhiro Takabayashi 等 5 人：“Na_2C_<60> 中 50 K 时的金属-绝缘体转变”B59(23) (1999)。

Y.Kubozono et al.: "Structure and Physical Properties of Na_4C_<60> under Ambient and High Pressures"Physical Review. B63. 45418-45426 (2001)

Y.Kubozono 等人：“环境压力和高压下 Na_4C_<60> 的结构和物理性质”物理评论。

井上崇・久保園芳博 他7名: "XAFS Study on Eu@C_<60>"Journal of Synchrotron Radiation. 6. 779-780 (1999)

Takashi Inoue、Yoshihiro Kubozono 等 7 人：“Eu@C_<60> 的 XAFS 研究”同步辐射杂志 6. 779-780 (1999)。

S.Fujiki, Y.Kubozono et al.: "Structure and Raman Scattering of Cs_3C_<60> under High Pressure"Physical Review. B62. 5366-5369 (2000)

S.Fujiki、Y.Kubozono 等人：“高压下 Cs_3C_<60> 的结构和拉曼散射”物理评论。