Doping-Mediated Energy-Level Engineering of M@Au12 Superatoms (M=Pd, Pt, Rh, Ir) for Efficient Photoluminescence and Photocatalysis

被引：106

作者：

Hirai, Haru ^{[1
]}

Takano, Shinjiro ^{[1
]}

Nakashima, Takuya ^{[2
]}

Iwasa, Takeshi ^{[3
,4
,5
]}

Taketsugu, Tetsuya ^{[3
,4
,5
]}

Tsukuda, Tatsuya ^{[1
,5
]}

机构：

[1] Univ Tokyo, Grad Sch Sci, Dept Chem, 7-3-1 Hongo,Bunkyo Ku, Tokyo 1130033, Japan

[2] Nara Inst Sci & Technol NAIST, Div Mat Sci, Nara 6300192, Japan

[3] Hokkaido Univ, Dept Chem, Fac Sci, Sapporo, Hokkaido 0600810, Japan

[4] Hokkaido Univ, Inst Chem React Design & Discovery WPI ICReDD, Sapporo, Hokkaido 0010021, Japan

[5] Kyoto Univ, Elements Strategy Initiat Catalysts & Batteries E, Kyoto 6158520, Japan

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2022年 / 61卷 / 36期

关键词：

Cluster Compounds; Doping Effects; Luminescence; Phosphine-Protected Gold Clusters; Superatoms; PHOTOREDOX CATALYSIS; CRYSTAL-STRUCTURE; GOLD CLUSTERS; LIGHT; NANOCLUSTERS;

D O I：

10.1002/anie.202207290

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We synthesized a series of MAu12(dppe)(5)Cl-2 (MAu12; M=Au, Pd, Pt, Rh, or Ir; dppe=1,2-bis(diphenylphosphino)ethane), which have icosahedral M@Au-12 superatomic cores, and systematically investigated their electronic structures, photoluminescence (PL) and photocatalytic properties. The energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) was expanded when doping an M element positioned at the lower left of the periodic table. The PL quantum yield was enhanced with an increase in the HOMO-LUMO gap and reached 0.46-0.67 for MAu12 (M=Pt, Rh, or Ir) under deaerated conditions. The bright PLs from MAu12 (M=Pt, Rh, or Ir) were assigned to phosphorescence based on quenching by O-2. MAu12 (M=Pt, Rh, or Ir) acted as a more efficient and stable photocatalyst than Au-13 for intramolecular [2+2] cycloaddition of bisenone via the oxidative quenching cycle. This study provides rational guides for designing photoluminescent and photocatalytic gold superatoms by the doping of heterometal elements.

引用

页数：8

共 50 条

[1] Electronic and Geometric Structure, Optical Properties, and Excited State Behavior in Atomically Precise Thiolate-Stabilized Noble Metal Nanoclusters [J].