TY - JOUR
T1 - [Cu15(PPh3)6(PET)13]2+
T2 - a Copper Nanocluster with Crystallization Enhanced Photoluminescence
AU - Nematulloev, Saidkhodzha
AU - Huang, Ren Wu
AU - Yin, Jun
AU - Shkurenko, Aleksander
AU - Dong, Chunwei
AU - Ghosh, Atanu
AU - Alamer, Badriah
AU - Naphade, Rounak
AU - Hedhili, Mohamed Nejib
AU - Maity, Partha
AU - Eddaoudi, Mohamed
AU - Mohammed, Omar F.
AU - Bakr, Osman M.
N1 - Funding Information:
This work was supported by King Abdullah University of Science and Technology (KAUST).
Publisher Copyright:
© 2021 Wiley-VCH GmbH
PY - 2021/7/8
Y1 - 2021/7/8
N2 - 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 [Cu15(PPh3)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 Cu6 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 C-H···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.
AB - 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 [Cu15(PPh3)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 Cu6 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 C-H···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.
KW - copper nanoclusters
KW - crystallization-induced emission enhancement
KW - near-infrared luminescence
KW - single crystals
UR - http://www.scopus.com/inward/record.url?scp=85102752227&partnerID=8YFLogxK
U2 - 10.1002/smll.202006839
DO - 10.1002/smll.202006839
M3 - Journal article
C2 - 33739606
AN - SCOPUS:85102752227
SN - 1613-6810
VL - 17
JO - Small
JF - Small
IS - 27
M1 - 2006839
ER -