基于钬的混合金属氮化物团簇富勒烯的合成、分离及光谱特性：HoxSc3-xN@C80（x=1,2）。

Synthesis, isolation, and spectroscopic characterization of holmium-based mixed-metal nitride clusterfullerenes: HoxSc3-xN@C80 (x=1, 2).

机构信息

Group of Electrochemistry and Conducting Polymers, Leibniz-Institute for Solid State and Materials Research (IFW) Dresden, 101171 Dresden, Germany.

出版信息

Chemistry. 2012 Jul 27;18(31):9691-8. doi: 10.1002/chem.201200574. Epub 2012 Jun 28.

DOI:10.1002/chem.201200574

PMID:22745152

Abstract

The synthesis, isolation and spectroscopic characterization of holmium-based mixed metal nitride clusterfullerenes Ho(x) Sc(3-x) N@C(80) (x=1, 2) are reported. Two isomers of Ho(x) Sc(3-x) N@C(80) (x=1, 2) were synthesized by the reactive gas atmosphere method and isolated by multistep recycling HPLC. The isomeric structures of Ho(x) Sc(3-x) N@C(80) (x=1, 2) were characterized by laser-desorption time-of-flight (LD-TOF) mass spectrometry and UV/Vis/NIR, FTIR and Raman spectroscopy. A comparative study of M(x) Sc(3-x) N@C(80) (M=Gd, Dy, Lu, Ho) demonstrates the dependence of their electronic and vibrational properties on the encaged metal. Despite the distinct perturbation induced by 4f(10) electrons, we report the first paramagnetic (13) C NMR study on Ho(x) Sc(3-x) N@C(80) (I; x=1, 2) and confirm I(h) -symmetric cage structure. A (45) Sc NMR study on HoSc(2) N@C(80) (I, II) revealed a temperature-dependent chemical shift in the temperature range of 268-308 K.

摘要

报道了基于钬的混合金属氮化物团簇富勒烯 Ho(x) Sc(3-x) N@C(80) (x=1, 2) 的合成、分离和光谱特性。通过反应气体气氛法合成了两种 Ho(x) Sc(3-x) N@C(80) (x=1, 2) 的异构体，并通过多步循环 HPLC 进行了分离。Ho(x) Sc(3-x) N@C(80) (x=1, 2) 的异构体结构通过激光解吸飞行时间（LD-TOF）质谱和 UV/Vis/NIR、FTIR 和拉曼光谱进行了表征。对 M(x) Sc(3-x) N@C(80) (M=Gd、Dy、Lu、Ho) 的比较研究表明，它们的电子和振动性质取决于笼内金属。尽管 4f(10) 电子引起了明显的扰动，但我们报告了首例对 Ho(x) Sc(3-x) N@C(80) (I; x=1, 2) 的顺磁 (13) C NMR 研究，并证实了 I(h)对称笼结构。对 HoSc(2) N@C(80) (I、II)的 (45) Sc NMR 研究表明，在 268-308 K 的温度范围内化学位移随温度变化。