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Title: Structural distortion and electron redistribution in dual-emitting gold nanoclusters

Abstract

Deciphering the complicated excited-state process is critical for the development of luminescent materials with controllable emissions in different applications. Here we report the emergence of a photo-induced structural distortion accompanied by an electron redistribution in a series of gold nanoclusters. Such unexpected slow process of excited-state transformation results in near-infrared dual emission with extended photoluminescent lifetime. We demonstrate that this dual emission exhibits highly sensitive and ratiometric response to solvent polarity, viscosity, temperature and pressure. Thus, a versatile luminescent nano-sensor for multiple environmental parameters is developed based on this strategy. Furthermore, we fully unravel the atomic-scale structural origin of this unexpected excited-state transformation, and demonstrate control over the transition dynamics by tailoring the bi-tetrahedral core structures of gold nanoclusters. Overall, this work provides a substantial advance in the excited-state physical chemistry of luminescent nanoclusters and a general strategy for the rational design of next-generation nano-probes, sensors and switches.

Authors:
 [1];  [2];  [3]; ORCiD logo [3]; ORCiD logo [4];  [5];  [3]; ORCiD logo [4];  [5]; ORCiD logo [6]; ORCiD logo [2]; ORCiD logo [3]
  1. Carnegie Mellon Univ., Pittsburgh, PA (United States); Stanford Univ., CA (United States)
  2. Zhejiang Univ., Hangzhou (China)
  3. Carnegie Mellon Univ., Pittsburgh, PA (United States)
  4. Brown Univ., Providence, RI (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States)
  6. Stanford Univ., CA (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1635476
Report Number(s):
BNL-216094-2020-JAAM
Journal ID: ISSN 2041-1723
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 11; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Li, Qi, Zhou, Dongming, Chai, Jinsong, So, Woong Young, Cai, Tong, Li, Mingxing, Peteanu, Linda A., Chen, Ou, Cotlet, Mircea, Wendy Gu, X., Zhu, Haiming, and Jin, Rongchao. Structural distortion and electron redistribution in dual-emitting gold nanoclusters. United States: N. p., 2020. Web. https://doi.org/10.1038/s41467-020-16686-8.
Li, Qi, Zhou, Dongming, Chai, Jinsong, So, Woong Young, Cai, Tong, Li, Mingxing, Peteanu, Linda A., Chen, Ou, Cotlet, Mircea, Wendy Gu, X., Zhu, Haiming, & Jin, Rongchao. Structural distortion and electron redistribution in dual-emitting gold nanoclusters. United States. https://doi.org/10.1038/s41467-020-16686-8
Li, Qi, Zhou, Dongming, Chai, Jinsong, So, Woong Young, Cai, Tong, Li, Mingxing, Peteanu, Linda A., Chen, Ou, Cotlet, Mircea, Wendy Gu, X., Zhu, Haiming, and Jin, Rongchao. Tue . "Structural distortion and electron redistribution in dual-emitting gold nanoclusters". United States. https://doi.org/10.1038/s41467-020-16686-8. https://www.osti.gov/servlets/purl/1635476.
@article{osti_1635476,
title = {Structural distortion and electron redistribution in dual-emitting gold nanoclusters},
author = {Li, Qi and Zhou, Dongming and Chai, Jinsong and So, Woong Young and Cai, Tong and Li, Mingxing and Peteanu, Linda A. and Chen, Ou and Cotlet, Mircea and Wendy Gu, X. and Zhu, Haiming and Jin, Rongchao},
abstractNote = {Deciphering the complicated excited-state process is critical for the development of luminescent materials with controllable emissions in different applications. Here we report the emergence of a photo-induced structural distortion accompanied by an electron redistribution in a series of gold nanoclusters. Such unexpected slow process of excited-state transformation results in near-infrared dual emission with extended photoluminescent lifetime. We demonstrate that this dual emission exhibits highly sensitive and ratiometric response to solvent polarity, viscosity, temperature and pressure. Thus, a versatile luminescent nano-sensor for multiple environmental parameters is developed based on this strategy. Furthermore, we fully unravel the atomic-scale structural origin of this unexpected excited-state transformation, and demonstrate control over the transition dynamics by tailoring the bi-tetrahedral core structures of gold nanoclusters. Overall, this work provides a substantial advance in the excited-state physical chemistry of luminescent nanoclusters and a general strategy for the rational design of next-generation nano-probes, sensors and switches.},
doi = {10.1038/s41467-020-16686-8},
journal = {Nature Communications},
number = 1,
volume = 11,
place = {United States},
year = {2020},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Fig. 1 Fig. 1: Optical properties and PL dynamics of Au24. (a) Anatomy of the atomic structure of Au24 determined by single-crystal X-ray diffraction. Purple=Core Au; Magenta=Surface Au; Yellow=S; Carbon tails are omitted for clarity. (b) UV-Vis absorption (black) and PL (grey) spectra (the asterisk denotes the spectrum “structuration” which is inducedmore » by the solvent). (c) PL excitation spectra for the two emissions, measured at 650 nm (blue) and 1050 nm (red), respectively. (d) and (e) Time-correlated-single-photon-counting (TCSPC) trajectories of the PL I (detected from 550 to 750 nm) and PL II (detected from 900 to 1000 nm). (f) Comparison of the TCSPC trajectories of PL I (blue) and PL II (red) in the early 1.5 ns. PL=photoluminescence. τ=PL lifetime component.« less

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