Au25 Clusters Containing Unoxidized Tellurolates in the Ligand Shell.
We report herein the synthesis and characterization of Au25 clusters containing tellurolates (TePh) in the ligand shell ([Au25(TePh)n(SC8H17)18-n](-); n = 1-18). [Au25(TePh)n(SC8H17)18-n](-) clusters were synthesized by reacting [Au25(SC8H17)18](-) with diphenyl ditelluride ((PhTe)2) in solution. Characterization of the products by mass spectrometry and X-ray absorption fine structure analysis revealed that the tellurolates in [Au25(TePh)n(SC8H17)18-n](-), unlike those in tellurolate-protected gold nanoparticles, were not oxidized. Various experiments on the products and theoretical calculations on related clusters revealed that protection by the tellurolates distorts (expands) the central Au13 core and decreases the HOMO-LUMO gap of the Au25 clusters.
†Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
Wataru
W
Kurashige
‡Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.|§Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto 615-8520, Japan.
Seiji
S
Yamazoe
†Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
Masaki
M
Yamaguchi
†Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
Keisuke
K
Nishido
§Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto 615-8520, Japan.
Katsuyuki
K
Nobusada
‡Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.|§Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto 615-8520, Japan.
Tatsuya
T
Tsukuda
†Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.|#Photocatalysis International Research Center, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan.
Yuichi
Y
Negishi
Au25 cluster; electronic structure; geometric structure; mass spectrometry; synthesis; tellurolate-protected gold clusters