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Title: 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 Au 13 core. The nanoclusters are characterized and formulated as [Au 13(dppe) 5Cl 2]Cl 3 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 C 1. Therefore, dppe ligands perform as a directing agent to create chiral an ansa metallamacrocycle [Au 13(dppe) 5Cl 2] 3+ nanocluster, as confirmed by simulated electronic circular dichroism spectrum. The highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap of the [Au 13(dppe) 5Cl 2] 3+ cluster is determined as approx. 1.9 eV, and further confirmed by ultraviolet photoemission spectroscopy analysis and DFT simulation. Furthermore, the photoactivity of [Au 13(dppe) 5Cl 2] 3+ is investigated, with the nanocluster shown to possess near-infrared photoluminescence properties, which can be employed for 1O 2 photogeneration. In conclusion, the quantum yield of 1O 2 photogeneration using the [Au 13(dppe) 5Cl 2] 3+ nanocluster is up to 0.71, which is considerably higher thanmore » those of anthracene (an organic dye), and Au 25 and Au 38 nanoclusters.« less

Authors:
 [1];  [2];  [1];  [3];  [4];  [5];  [1]
  1. Chinese Academy of Sciences, Dalian (China). State Key Lab. of Catalysis, Dalian Inst. of Chemical Physics
  2. Chinese Academy of Sciences, Dalian (China). State Key Lab. of Catalysis, Dalian Inst. of Chemical Physics; Univ. of Chinese Academy of Sciences, Beijing (China)
  3. Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Dept. of Chemical Engineering
  4. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
  5. Peking Univ., Beijing (China). Beijing National Lab. for Molecular Sciences, State Key Lab. of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering
Publication Date:
Research Org.:
National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States). In-house Research
Sponsoring Org.:
USDOE
OSTI Identifier:
1477163
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:
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. doi: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. doi:10.1007/s12274-017-1935-2.
@article{osti_1477163,
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 = {2018},
month = {11}
}

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Works referenced in this record:

Density?functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913