TY - JOUR
T1 - Development of Integrated Dry-Wet Synthesis Method for Metal Encapsulating Silicon Cage Superatoms of M@Si16 (M = Ti and Ta)
AU - Tsunoyama, Hironori
AU - Akatsuka, Hiroki
AU - Shibuta, Masahiro
AU - Iwasa, Takeshi
AU - Mizuhata, Yoshiyuki
AU - Tokitoh, Norihiro
AU - Nakajima, Atsushi
N1 - Funding Information:
The work is financially supported partly by the JSPS KAKENHI Grant-in-Aid for Scientific Research (A) grant no. 15H02002 and by the Young Scientists (A) grant no. 15H05475. This study was supported by the Joint Usage/Research Center (JURC) at the Institute for Chemical Research, Kyoto University, by providing access to a Bruker Advance III 800US Plus spectrometer. We are grateful to Mr. K. Tsukamoto (Ayabo Corp.) and Dr. S. Nagaoka for the construction of gas-phase NC source based on HiPIMS, to Prof. Dr. M. Hada for discussion about theoretical treatments of 29Si chemical shifts, to Ms. A. Maeno and Ms. K. Ohmine (ICR, Kyoto University) for 29Si NMR measurements, and to Ms. Y. Asada, Ms. K. Kobayashi, and Ms. M. Ito for mass production and isolation of M@Si16:PEG-DME.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/9/21
Y1 - 2017/9/21
N2 - Nanoclusters (NCs) of several to hundreds of atoms in size are prospective functional units for future nanomaterials originating in their unique, size-specific properties. To explore the field of NC-based materials science, the development of large-scale, size-exclusive synthesis methods is in high demand, as one can see from the successful evolution of fullerene science. We have developed a large-scale synthesis method for main group-based NC compounds by scaling up the clean dry-process with a high-power impulse magnetron sputtering. The 100 mg scale synthesis of binary NCs of M@Si16 (M = Ti and Ta) stabilized by poly(ethylene glycol) dimethyl ether enables us to characterize their structures by an array of methods, for example, mass spectroscopy, X-ray photoemission spectroscopy, Raman spectroscopy, and 29Si nuclear magnetic resonance. Spectroscopic evidence indicates that the M@Si16 NCs are the metal-encapsulating tetrahedral silicon-cage structure satisfying the 68 electrons, closed-electronic-shell superatom.
AB - Nanoclusters (NCs) of several to hundreds of atoms in size are prospective functional units for future nanomaterials originating in their unique, size-specific properties. To explore the field of NC-based materials science, the development of large-scale, size-exclusive synthesis methods is in high demand, as one can see from the successful evolution of fullerene science. We have developed a large-scale synthesis method for main group-based NC compounds by scaling up the clean dry-process with a high-power impulse magnetron sputtering. The 100 mg scale synthesis of binary NCs of M@Si16 (M = Ti and Ta) stabilized by poly(ethylene glycol) dimethyl ether enables us to characterize their structures by an array of methods, for example, mass spectroscopy, X-ray photoemission spectroscopy, Raman spectroscopy, and 29Si nuclear magnetic resonance. Spectroscopic evidence indicates that the M@Si16 NCs are the metal-encapsulating tetrahedral silicon-cage structure satisfying the 68 electrons, closed-electronic-shell superatom.
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U2 - 10.1021/acs.jpcc.7b06449
DO - 10.1021/acs.jpcc.7b06449
M3 - Article
AN - SCOPUS:85029764581
SN - 1932-7447
VL - 121
SP - 20507
EP - 20516
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 37
ER -