(AuAg)44(SPhtBu)26 versus (AuAg)44(SPhF2)30: Tailoring the Geometric Structures and Optical Properties of Nanocluster Analogues

Monolayer-protected nanoclusters are ideal models for understanding the correlations between structures and properties of inorganic nanoparticles, especially for those molecules with identical sizes but comparable structures. Here, we controllably prepared and structurally determined a valence-neutr...

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Main Authors: Jiaojiao Han, Hao Li, Honglei Shen, Ying Xu, Xuejuan Zou, Xi Kang, Manzhou Zhu
Format: Article
Language:English
Published: American Chemical Society 2023-03-01
Series:Precision Chemistry
Online Access:https://doi.org/10.1021/prechem.2c00007
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author Jiaojiao Han
Hao Li
Honglei Shen
Ying Xu
Xuejuan Zou
Xi Kang
Manzhou Zhu
author_facet Jiaojiao Han
Hao Li
Honglei Shen
Ying Xu
Xuejuan Zou
Xi Kang
Manzhou Zhu
author_sort Jiaojiao Han
collection DOAJ
description Monolayer-protected nanoclusters are ideal models for understanding the correlations between structures and properties of inorganic nanoparticles, especially for those molecules with identical sizes but comparable structures. Here, we controllably prepared and structurally determined a valence-neutral Au24+xAg20‑x(SPhtBu)26 (0 < x < 4) nanocluster with comparable structure features to a well-known Au12Ag32(SPhF2)30 cluster. The Au24+xAg20‑x(SPhtBu)26 cluster contained a hollow Au12@M20 metallic kernel (M = Au/Ag), 12 Au1(SR)2 staples, and two bridging SR molecules, and its average molecular formula was determined to be Au26.3Ag17.7(SPhtBu)26, as evidenced by X-ray crystallography and electrospray ionization mass spectrometry. Because of the ligand effect and the asymmetrical arrangement of the Au dopants in the dodecahedral cage, the Au24+xAg20‑x(SPhtBu)26 nanocluster exhibited lower molecular symmetry relative to Au12Ag32(SPhF2)30 in terms of the dodecahedral kernel and motif shell structures. Besides, the strong π–π interaction in Au24+xAg20‑x(SPhtBu)26 contributed to its enhanced photoluminescence intensity compared with Au12Ag32(SPhF2)30. The study, herein, extends the 44-metal-atom cluster family, thereby enabling us to better understand the correlations between their structures and properties at the atomic level.
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spelling doaj.art-42fc6220937a492fb490d7f6e85f57632023-08-21T17:59:25ZengAmerican Chemical SocietyPrecision Chemistry2771-93162023-03-011313914510.1021/prechem.2c00007(AuAg)44(SPhtBu)26 versus (AuAg)44(SPhF2)30: Tailoring the Geometric Structures and Optical Properties of Nanocluster AnaloguesJiaojiao HanHao LiHonglei ShenYing XuXuejuan ZouXi KangManzhou ZhuMonolayer-protected nanoclusters are ideal models for understanding the correlations between structures and properties of inorganic nanoparticles, especially for those molecules with identical sizes but comparable structures. Here, we controllably prepared and structurally determined a valence-neutral Au24+xAg20‑x(SPhtBu)26 (0 < x < 4) nanocluster with comparable structure features to a well-known Au12Ag32(SPhF2)30 cluster. The Au24+xAg20‑x(SPhtBu)26 cluster contained a hollow Au12@M20 metallic kernel (M = Au/Ag), 12 Au1(SR)2 staples, and two bridging SR molecules, and its average molecular formula was determined to be Au26.3Ag17.7(SPhtBu)26, as evidenced by X-ray crystallography and electrospray ionization mass spectrometry. Because of the ligand effect and the asymmetrical arrangement of the Au dopants in the dodecahedral cage, the Au24+xAg20‑x(SPhtBu)26 nanocluster exhibited lower molecular symmetry relative to Au12Ag32(SPhF2)30 in terms of the dodecahedral kernel and motif shell structures. Besides, the strong π–π interaction in Au24+xAg20‑x(SPhtBu)26 contributed to its enhanced photoluminescence intensity compared with Au12Ag32(SPhF2)30. The study, herein, extends the 44-metal-atom cluster family, thereby enabling us to better understand the correlations between their structures and properties at the atomic level.https://doi.org/10.1021/prechem.2c00007
spellingShingle Jiaojiao Han
Hao Li
Honglei Shen
Ying Xu
Xuejuan Zou
Xi Kang
Manzhou Zhu
(AuAg)44(SPhtBu)26 versus (AuAg)44(SPhF2)30: Tailoring the Geometric Structures and Optical Properties of Nanocluster Analogues
Precision Chemistry
title (AuAg)44(SPhtBu)26 versus (AuAg)44(SPhF2)30: Tailoring the Geometric Structures and Optical Properties of Nanocluster Analogues
title_full (AuAg)44(SPhtBu)26 versus (AuAg)44(SPhF2)30: Tailoring the Geometric Structures and Optical Properties of Nanocluster Analogues
title_fullStr (AuAg)44(SPhtBu)26 versus (AuAg)44(SPhF2)30: Tailoring the Geometric Structures and Optical Properties of Nanocluster Analogues
title_full_unstemmed (AuAg)44(SPhtBu)26 versus (AuAg)44(SPhF2)30: Tailoring the Geometric Structures and Optical Properties of Nanocluster Analogues
title_short (AuAg)44(SPhtBu)26 versus (AuAg)44(SPhF2)30: Tailoring the Geometric Structures and Optical Properties of Nanocluster Analogues
title_sort auag 44 sphtbu 26 versus auag 44 sphf2 30 tailoring the geometric structures and optical properties of nanocluster analogues
url https://doi.org/10.1021/prechem.2c00007
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