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Heterometallation of Photoluminescent Silver(I) Sulfide Nanoclusters Protected by Octahedral Iridium(III) Thiolates
Author(s) -
Goo Zi Lang,
Minami Katsue,
Yoshinari Nobuto,
Konno Takumi
Publication year - 2021
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.202100706
Subject(s) - iridium , nanoclusters , octahedron , quantum yield , photoluminescence , crystallography , chemistry , cluster (spacecraft) , sulfide , metal , yield (engineering) , molecule , materials science , crystal structure , nanotechnology , fluorescence , physics , catalysis , biochemistry , optoelectronics , organic chemistry , quantum mechanics , computer science , programming language , metallurgy
The recently‐increasing interest in coinage metal clusters stems from their photophysical properties, which are controlled via heterometallation. Herein, we report homometallic Ag I 46 S 13 clusters protected by octahedral fac ‐[Ir(aet) 3 ] (aet=2‐aminoethanethiolate) molecules and their conversion to heterometallic Ag I 43 M I 3 S 13 (M=Cu, Au) clusters. The reactions of fac ‐[Ir(aet) 3 ] with Ag + and penicillamine produced [Ag 46 S 13 {Ir(aet) 3 } 14 ] 20+ ([ 1 ] 20+ ), where a spherical Ag I 46 S 13 cluster is covered by fac ‐[Ir(aet) 3 ] octahedra through thiolato bridges. [ 1 ] 20+ was converted to [Ag 43 M 3 S 13 {Ir(aet) 3 } 14 ] 20+ ([ 1 M ] 20+ ) with an Ag I 43 M I 3 S 13 cluster by treatment with M + , retaining its overall structure. [ 1 ] 20+ was photoluminescent and had an emission band ca. 690 nm that originated from an S‐to‐Ag charge transfer. While [ 1 Cu ] 20+ showed an emission band with a slightly higher energy of ca. 650 nm and a lower quantum yield, the emission band for [ 1 Au ] 20+ shifted to a much higher energy of ca. 590 nm with an enhanced quantum yield.