Carboranealkynyl‐Protected Gold Nanoclusters: Size Conversion and UV/Vis–NIR Optical Properties
Structure evolution has become an effective way to assemble novel monolayer‐protected metal nanomolecules. However, evolution with alkynyl‐stabilized metal clusters still remains rarely explored. Herein, we present a carboranealkynyl‐protected gold nanocluster [Au28(C4B10H11)12(tht)8]3+ (Au28, tht=t...
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| Published in | Angewandte Chemie International Edition Vol. 60; no. 11; pp. 5959 - 5964 |
|---|---|
| Main Authors | , , , , |
| Format | Journal Article |
| Language | English |
| Published |
Germany
Wiley Subscription Services, Inc
08.03.2021
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| Edition | International ed. in English |
| Subjects | |
| Online Access | Get full text |
| ISSN | 1433-7851 1521-3773 1521-3773 |
| DOI | 10.1002/anie.202013027 |
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| Abstract | Structure evolution has become an effective way to assemble novel monolayer‐protected metal nanomolecules. However, evolution with alkynyl‐stabilized metal clusters still remains rarely explored. Herein, we present a carboranealkynyl‐protected gold nanocluster [Au28(C4B10H11)12(tht)8]3+ (Au28, tht=tetrahydrothiophene) possessing an open‐shell electronic structure with 13 free electrons, which was isolated by a facile self‐reduction method with 9‐HC≡C‐closo‐1,2‐C2B10H11 as the two‐in‐one reducing and protecting agent. Notably, Au28 undergoes a complete transformation in methanol into a stable and smaller‐sized nanocluster [Au23(C4B10H11)9(tht)6]2+ (Au23) bearing 12 valence electrons and crystal‐field‐like split superatomic 1D orbitals. The transformation process was systematically monitored with ESI‐MS and UV/Vis absorption spectra. Au28 and Au23 both display optical absorption covering the UV/Vis–NIR range and NIR emission, which facilitates their potential application in the biomedical and photocatalytic fields.
A carboranealkynyl‐protected gold nanocluster Au28 possessing an open‐shell electronic structure with 13 valence electrons was isolated through a facile self‐reduction method in which it undergoes a complete transformation in methanol into a smaller‐sized cluster Au23 bearing 12 valence electrons and crystal‐field‐like split superatomic 1D orbitals. Au28 and Au23 both display optical absorption covering the UV/Vis–NIR range and NIR emission. |
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| AbstractList | Structure evolution has become an effective way to assemble novel monolayer-protected metal nanomolecules. However, evolution with alkynyl-stabilized metal clusters still remains rarely explored. Herein, we present a carboranealkynyl-protected gold nanocluster [Au28 (C4 B10 H11 )12 (tht)8 ]3+ (Au28 , tht=tetrahydrothiophene) possessing an open-shell electronic structure with 13 free electrons, which was isolated by a facile self-reduction method with 9-HC≡C-closo-1,2-C2 B10 H11 as the two-in-one reducing and protecting agent. Notably, Au28 undergoes a complete transformation in methanol into a stable and smaller-sized nanocluster [Au23 (C4 B10 H11 )9 (tht)6 ]2+ (Au23 ) bearing 12 valence electrons and crystal-field-like split superatomic 1D orbitals. The transformation process was systematically monitored with ESI-MS and UV/Vis absorption spectra. Au28 and Au23 both display optical absorption covering the UV/Vis-NIR range and NIR emission, which facilitates their potential application in the biomedical and photocatalytic fields.Structure evolution has become an effective way to assemble novel monolayer-protected metal nanomolecules. However, evolution with alkynyl-stabilized metal clusters still remains rarely explored. Herein, we present a carboranealkynyl-protected gold nanocluster [Au28 (C4 B10 H11 )12 (tht)8 ]3+ (Au28 , tht=tetrahydrothiophene) possessing an open-shell electronic structure with 13 free electrons, which was isolated by a facile self-reduction method with 9-HC≡C-closo-1,2-C2 B10 H11 as the two-in-one reducing and protecting agent. Notably, Au28 undergoes a complete transformation in methanol into a stable and smaller-sized nanocluster [Au23 (C4 B10 H11 )9 (tht)6 ]2+ (Au23 ) bearing 12 valence electrons and crystal-field-like split superatomic 1D orbitals. The transformation process was systematically monitored with ESI-MS and UV/Vis absorption spectra. Au28 and Au23 both display optical absorption covering the UV/Vis-NIR range and NIR emission, which facilitates their potential application in the biomedical and photocatalytic fields. Structure evolution has become an effective way to assemble novel monolayer‐protected metal nanomolecules. However, evolution with alkynyl‐stabilized metal clusters still remains rarely explored. Herein, we present a carboranealkynyl‐protected gold nanocluster [Au 28 (C 4 B 10 H 11 ) 12 (tht) 8 ] 3+ ( Au 28 , tht=tetrahydrothiophene) possessing an open‐shell electronic structure with 13 free electrons, which was isolated by a facile self‐reduction method with 9‐HC≡C‐ closo ‐1,2‐C 2 B 10 H 11 as the two‐in‐one reducing and protecting agent. Notably, Au 28 undergoes a complete transformation in methanol into a stable and smaller‐sized nanocluster [Au 23 (C 4 B 10 H 11 ) 9 (tht) 6 ] 2+ ( Au 23 ) bearing 12 valence electrons and crystal‐field‐like split superatomic 1D orbitals. The transformation process was systematically monitored with ESI‐MS and UV/Vis absorption spectra. Au 28 and Au 23 both display optical absorption covering the UV/Vis–NIR range and NIR emission, which facilitates their potential application in the biomedical and photocatalytic fields. Structure evolution has become an effective way to assemble novel monolayer‐protected metal nanomolecules. However, evolution with alkynyl‐stabilized metal clusters still remains rarely explored. Herein, we present a carboranealkynyl‐protected gold nanocluster [Au28(C4B10H11)12(tht)8]3+ (Au28, tht=tetrahydrothiophene) possessing an open‐shell electronic structure with 13 free electrons, which was isolated by a facile self‐reduction method with 9‐HC≡C‐closo‐1,2‐C2B10H11 as the two‐in‐one reducing and protecting agent. Notably, Au28 undergoes a complete transformation in methanol into a stable and smaller‐sized nanocluster [Au23(C4B10H11)9(tht)6]2+ (Au23) bearing 12 valence electrons and crystal‐field‐like split superatomic 1D orbitals. The transformation process was systematically monitored with ESI‐MS and UV/Vis absorption spectra. Au28 and Au23 both display optical absorption covering the UV/Vis–NIR range and NIR emission, which facilitates their potential application in the biomedical and photocatalytic fields. A carboranealkynyl‐protected gold nanocluster Au28 possessing an open‐shell electronic structure with 13 valence electrons was isolated through a facile self‐reduction method in which it undergoes a complete transformation in methanol into a smaller‐sized cluster Au23 bearing 12 valence electrons and crystal‐field‐like split superatomic 1D orbitals. Au28 and Au23 both display optical absorption covering the UV/Vis–NIR range and NIR emission. Structure evolution has become an effective way to assemble novel monolayer‐protected metal nanomolecules. However, evolution with alkynyl‐stabilized metal clusters still remains rarely explored. Herein, we present a carboranealkynyl‐protected gold nanocluster [Au28(C4B10H11)12(tht)8]3+ (Au28, tht=tetrahydrothiophene) possessing an open‐shell electronic structure with 13 free electrons, which was isolated by a facile self‐reduction method with 9‐HC≡C‐closo‐1,2‐C2B10H11 as the two‐in‐one reducing and protecting agent. Notably, Au28 undergoes a complete transformation in methanol into a stable and smaller‐sized nanocluster [Au23(C4B10H11)9(tht)6]2+ (Au23) bearing 12 valence electrons and crystal‐field‐like split superatomic 1D orbitals. The transformation process was systematically monitored with ESI‐MS and UV/Vis absorption spectra. Au28 and Au23 both display optical absorption covering the UV/Vis–NIR range and NIR emission, which facilitates their potential application in the biomedical and photocatalytic fields. Structure evolution has become an effective way to assemble novel monolayer-protected metal nanomolecules. However, evolution with alkynyl-stabilized metal clusters still remains rarely explored. Herein, we present a carboranealkynyl-protected gold nanocluster [Au (C B H ) (tht) ] (Au , tht=tetrahydrothiophene) possessing an open-shell electronic structure with 13 free electrons, which was isolated by a facile self-reduction method with 9-HC≡C-closo-1,2-C B H as the two-in-one reducing and protecting agent. Notably, Au undergoes a complete transformation in methanol into a stable and smaller-sized nanocluster [Au (C B H ) (tht) ] (Au ) bearing 12 valence electrons and crystal-field-like split superatomic 1D orbitals. The transformation process was systematically monitored with ESI-MS and UV/Vis absorption spectra. Au and Au both display optical absorption covering the UV/Vis-NIR range and NIR emission, which facilitates their potential application in the biomedical and photocatalytic fields. |
| Author | Li, Shi‐Jun Zang, Shuang‐Quan Mak, Thomas C. W. Wang, Zhao‐Yang Wang, Jie |
| Author_xml | – sequence: 1 givenname: Jie surname: Wang fullname: Wang, Jie organization: Zhengzhou University – sequence: 2 givenname: Zhao‐Yang surname: Wang fullname: Wang, Zhao‐Yang email: wangzy@zzu.edu.cn organization: Zhengzhou University – sequence: 3 givenname: Shi‐Jun surname: Li fullname: Li, Shi‐Jun organization: Zhengzhou University – sequence: 4 givenname: Shuang‐Quan orcidid: 0000-0002-6728-0559 surname: Zang fullname: Zang, Shuang‐Quan email: zangsqzg@zzu.edu.cn organization: Zhengzhou University – sequence: 5 givenname: Thomas C. W. surname: Mak fullname: Mak, Thomas C. W. organization: The Chinese University of Hong Kong |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/33314503$$D View this record in MEDLINE/PubMed |
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| Keywords | NIR emission structure evolution self-reduction syntheses carboranes gold nanoclusters |
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| Snippet | Structure evolution has become an effective way to assemble novel monolayer‐protected metal nanomolecules. However, evolution with alkynyl‐stabilized metal... Structure evolution has become an effective way to assemble novel monolayer-protected metal nanomolecules. However, evolution with alkynyl-stabilized metal... |
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| SubjectTerms | Absorption Absorption spectra carboranes Electronic structure Evolution Free electrons Gold gold nanoclusters Metal clusters Nanoclusters NIR emission Optical properties self-reduction syntheses structure evolution |
| Title | Carboranealkynyl‐Protected Gold Nanoclusters: Size Conversion and UV/Vis–NIR Optical Properties |
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