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Title: Diphosphine-induced chiral propeller arrangement of gold nanoclusters for singlet oxygen photogeneration

Journal Article · · Nano Research
 [1];  [2];  [1];  [3];  [4];  [5];  [1]
  1. Chinese Academy of Sciences, Dalian (China)
  2. Chinese Academy of Sciences, Dalian (China); Univ. of Chinese Academy of Sciences, Beijing (China)
  3. Stanford Univ., Stanford, CA (United States)
  4. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
  5. Peking Univ., Beijing (China)
+ Show Author Affiliations

In this study, 1,2-bis(diphenylphosphino)ethane (dppe) ligands are used to synthesize gold nanoclusters with an icosahedral Au13 core. The nanoclusters are characterized and formulated as [Au13(dppe)5Cl2]Cl3 using synchrotron radiation X-ray diffraction, UV/Vis absorption spectroscopy, electrospray ionization mass spectrometry, and density functional theory (DFT) calculations. The bidentate feature of dppe ligands and the positions of coordinating surface gold atoms induce a helical arrangement that forms a propeller-like structure, which reduces the symmetry of the gold nanocluster to C1. Therefore, dppe ligands perform as a directing agent to create chiral an ansa metallamacrocycle [Au13(dppe)5Cl2]3+ nanocluster, as confirmed by simulated electronic circular dichroism spectrum. The highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap of the [Au13(dppe)5Cl2]3+ cluster is determined as approx. 1.9 eV, and further confirmed by ultraviolet photoemission spectroscopy analysis and DFT simulation. Furthermore, the photoactivity of [Au13(dppe)5Cl2]3+ is investigated, with the nanocluster shown to possess near-infrared photoluminescence properties, which can be employed for 1O2 photogeneration. In conclusion, the quantum yield of 1O2 photogeneration using the [Au13(dppe)5Cl2]3+ nanocluster is up to 0.71, which is considerably higher than those of anthracene (an organic dye), and Au25 and Au38 nanoclusters.

Research Organization:
National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States); National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States). In-house Research
Sponsoring Organization:
FE; USDOE
OSTI ID:
1509723
Alternate ID(s):
OSTI ID: 1477163
Report Number(s):
NETL-PUB-22331
Journal Information:
Nano Research, Vol. 11, Issue 11; ISSN 1998-0124
Publisher:
SpringerCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

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Cited By (6)

Tailoring the stability, photocatalysis and photoluminescence properties of Au 11 nanoclusters via doping engineering journal January 2019
Heterogeneous Cross-Coupling over Gold Nanoclusters journal June 2019
Supramolecular topology design of silver( i ) and copper( ii ) coordination polymers through a new semi-rigid sulfonyl ligand with different anion templates journal January 2019
Motif-mediated Au25(SPh)5(PPh3)10X2 nanorods with conjugated electron delocalization journal August 2018
Chirality in Au 9 clusters protected by chiral/achiral mixed bidentate phosphine ligands: influence of the metal core and ligand array journal January 2019
Potential of N-heterocyclic carbene derivatives from Au 13 (dppe) 5 Cl 2 gold superatoms. Evaluation of electronic, optical and chiroptical properties from relativistic DFT journal January 2019

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Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
36 MATERIALS SCIENCE
Catalyst development
nanomaterials
materials characterization
X-ray spectroscopy
photoluminescence