Diphosphine-induced chiral propeller arrangement of gold nanoclusters for singlet oxygen photogeneration
Abstract
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.
- Authors:
-
- Chinese Academy of Sciences, Dalian (China)
- Chinese Academy of Sciences, Dalian (China); Univ. of Chinese Academy of Sciences, Beijing (China)
- Stanford Univ., Stanford, CA (United States)
- National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
- Peking Univ., Beijing (China)
- Publication Date:
- Research Org.:
- 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 Org.:
- FE; USDOE
- OSTI Identifier:
- 1509723
- Alternate Identifier(s):
- OSTI ID: 1477163
- Report Number(s):
- NETL-PUB-22331
Journal ID: ISSN 1998-0124
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nano Research
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 11; Journal ID: ISSN 1998-0124
- Publisher:
- Springer
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 74 ATOMIC AND MOLECULAR PHYSICS; 36 MATERIALS SCIENCE; Catalyst development; nanomaterials; materials characterization; X-ray spectroscopy; photoluminescence
Citation Formats
Zhang, Jiangwei, Zhou, Yang, Zheng, Kai, Abroshan, Hadi, Kauffman, Douglas R., Sun, Junliang, and Li, Gao. Diphosphine-induced chiral propeller arrangement of gold nanoclusters for singlet oxygen photogeneration. United States: N. p., 2018.
Web. doi:10.1007/s12274-017-1935-2.
Zhang, Jiangwei, Zhou, Yang, Zheng, Kai, Abroshan, Hadi, Kauffman, Douglas R., Sun, Junliang, & Li, Gao. Diphosphine-induced chiral propeller arrangement of gold nanoclusters for singlet oxygen photogeneration. United States. https://doi.org/10.1007/s12274-017-1935-2
Zhang, Jiangwei, Zhou, Yang, Zheng, Kai, Abroshan, Hadi, Kauffman, Douglas R., Sun, Junliang, and Li, Gao. Mon .
"Diphosphine-induced chiral propeller arrangement of gold nanoclusters for singlet oxygen photogeneration". United States. https://doi.org/10.1007/s12274-017-1935-2. https://www.osti.gov/servlets/purl/1509723.
@article{osti_1509723,
title = {Diphosphine-induced chiral propeller arrangement of gold nanoclusters for singlet oxygen photogeneration},
author = {Zhang, Jiangwei and Zhou, Yang and Zheng, Kai and Abroshan, Hadi and Kauffman, Douglas R. and Sun, Junliang and Li, Gao},
abstractNote = {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.},
doi = {10.1007/s12274-017-1935-2},
journal = {Nano Research},
number = 11,
volume = 11,
place = {United States},
year = {Mon Nov 12 00:00:00 EST 2018},
month = {Mon Nov 12 00:00:00 EST 2018}
}
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