Premium
[Cu 15 (PPh 3 ) 6 (PET) 13 ] 2+ : a Copper Nanocluster with Crystallization Enhanced Photoluminescence
Author(s) -
Nematulloev Saidkhodzha,
Huang RenWu,
Yin Jun,
Shkurenko Aleksander,
Dong Chunwei,
Ghosh Atanu,
Alamer Badriah,
Naphade Rounak,
Hedhili Mohamed Nejib,
Maity Partha,
Eddaoudi Mohamed,
Mohammed Omar F.,
Bakr Osman M.
Publication year - 2021
Publication title -
small
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.785
H-Index - 236
eISSN - 1613-6829
pISSN - 1613-6810
DOI - 10.1002/smll.202006839
Subject(s) - nanoclusters , photoluminescence , materials science , crystallization , luminescence , intermolecular force , copper , intramolecular force , crystallography , ligand (biochemistry) , density functional theory , crystal structure , phosphine , nanotechnology , chemical physics , catalysis , molecule , chemistry , optoelectronics , computational chemistry , stereochemistry , biochemistry , receptor , organic chemistry , metallurgy
Due to their atomically precise structure, photoluminescent copper nanoclusters (Cu NCs) have emerged as promising materials in both fundamental studies and technological applications, such as bio‐imaging, cell labeling, phototherapy, and photo‐activated catalysis. In this work, a facile strategy is reported for the synthesis of a novel Cu NCs coprotected by thiolate and phosphine ligands, formulated as [Cu 15 (PPh 3 ) 6 (PET) 13 ] 2+ , which exhibits bright emission in the near‐infrared (NIR) region (≈720 nm) and crystallization‐induced emission enhancement (CIEE) phenomenon. Single crystal X‐ray crystallography shows that the NC possesses an extraordinary distorted trigonal antiprismatic Cu 6 core and a, unique among metal clusters, “tri‐blade fan”‐like structure. An in‐depth structural investigation of the ligand shell combined with density functional theory calculations reveal that the extended CH···π and π‐π intermolecular ligand interactions significantly restrict the intramolecular rotations and vibrations and, thus, are a major reason for the CIEE phenomena. This study provides a strategy for the controllable synthesis of structurally defined Cu NCs with NIR luminescence, which enables essential insights into the origins of their optical properties.