Molecular Location Sensing Approach by Anisotropic Magnetism of an Endohedral Metallofullerene.
Location recognition at the molecular scale provides valuable information about the nature of functional molecular materials. This study presents a novel location sensing approach based on an endohedral metallofullerene, Ce@C, using its anisotropic magnetic properties, which lead to temperature-depe...
| Publicado en: | Journal of the American Chemical Society Vol. 138; no. 25; pp. 8000 - 8007 |
|---|---|
| Autores principales: | , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
6/29/2016
|
| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=116882217&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 116882217 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 6/29/2016 vid: 138 iid: 25 pid: 997 pub: American Chemical Society artinfo: ui: 116882217 10.1021/jacs.6b04037 ppf: 8000 ppct: 7 formats: tig: atl: Molecular Location Sensing Approach by Anisotropic Magnetism of an Endohedral Metallofullerene. aug: au: Yuta Takano Ryo Tashita Mitsuaki Suzuki Shigeru Nagase Hiroshi Imahori Takeshi Akasaka affil: Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan TLife Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Tsukuba, Ibaraki 305-8577, Japan Department of Chemistry, Tokyo Gakugei University, Tokyo 184-8501, Japan Yukui Institute for Fundamental Chemistry, Kyoto University, Sakyo-ku, Kyoto 606-8103, Japan Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan State Key Laboratory of Materials Processing and Die & Mold Technology, School of Materials Science and Technology, Huazhong University of Science and Technology, Wuhan 430074, China Foundation for Advancement of International Science, Tsukuba, Ibaraki 305-0821, Japan su: Metallofullerenes Anisotropic crystals Enhanced magnetoresistance Density functional theory Magnetic anisotropy Gaussian channels sug: subj: Metallofullerenes Anisotropic crystals Enhanced magnetoresistance Density functional theory Magnetic anisotropy Gaussian channels ab: Location recognition at the molecular scale provides valuable information about the nature of functional molecular materials. This study presents a novel location sensing approach based on an endohedral metallofullerene, Ce@C, using its anisotropic magnetic properties, which lead to temperature-dependent paramagnetic shifts in H NMR spectra. Five site-isomers of Ce@CCH-3,5-CHMe were synthesized to demonstrate the spatial sensing ability of Ce@C. Single-crystal structures, absorption spectra, and density functional theory calculations were used to select the plausible addition positions in the radical coupling reaction, which preferentially happens on the carbon atoms with high electron density of the singly occupied molecular orbital (SOMO) and positive charge. Temperature-dependent NMR measurements demonstrated unique paramagnetic shifts of the 1H peaks, which were derived from the anisotropic magnetism of the f-electron in the Ce atom of the isomers. It was found that the magnetic anisotropy axes can be easily predicted by theoretical calculations using the Gaussian 09 package. Further analysis revealed that the temperature-dependent trend in the shifts is clearly predictable from the distance and relative position of the proton from the Ce atom. Hence, the Ce-encapsulated metallofullerene Ce@C can provide spatial location information about nearby atoms through the temperature-dependent paramagnetic shifts of its NMR signals. It can act as a molecular probe for location sensing by utilizing the anisotropic magnetism of the encapsulated Ce atom. The potentially low toxicity and stability of the endohedral fullerene would make Ce@C suitable for applications in biology and material science. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2016 holdings: @attributes: islocal: N |
|---|