AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Superatomic Au13 clusters ligated by different N-heterocyclic carbenes and their ligand-dependent catalysis, photoluminescence, and proton sensitivity

Hui Shen1, Sijin Xiang1, Zhen Xu1, Chen Liu2, Xihua Li1, Cunfa Sun1, Shuichao Lin1, Boon K. Teo1, Nanfeng Zheng1( )
State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National & Local Joint Engineering Research Center of Preparation Technology of Nanomaterials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
School of Pharmaceutical Science, Xiamen University, Xiamen 361002, China
Show Author Information

Graphical Abstract

Abstract

We report herein a class of superatomic Au13 clusters stabilized by different N-heterocyclic carbenes (NHCs). The clusters show diverse metal surface structures, properties and functions as exemplified by: (1) the first anionic Au13 cluster [Au13(NHC-1)6Br6]-, which has bulky NHC-1 ligands that lead to a rather open metal surface contributing to its high catalytic activity; (2) the tricationic cluster [Au13(NHC-2)5Br2]3+ which has bidentate, benzyl-rich NHC-2 ligands that make it ultra-stable and highly-luminescent, suitable for bio-imaging; and (3) by bearing two pyridyl groups on NHC-3, the dicationic cluster [Au13(NHC-3)9Cl3]2+ exhibits reversible and stable visible absorption and solubility responses to protonation/deprotonation cycles, making it a potential pH sensor (NHC-1 = 1,3-diisopropylbenzimidazolin-2-ylidene; NHC-2 = 1,3-bis(1-benzyl-1H-benzimidazol-1-ium-3-yl)propane; NHC-3 = 1,3-bis(picolyl)benzimidazolin-2-ylidene). The study nicely demonstrates the importance of ligands in designing metal nanoclusters with desired functionalities.

Keywords

carbene ligandsgold nanoclustercatalysisluminescenceAu13

Electronic Supplementary Material

Download File(s)
12274_2020_2685_MOESM1_ESM.cif (2.3 MB)
12274_2020_2685_MOESM2_ESM.cif (18.4 MB)
12274_2020_2685_MOESM3_ESM.cif (3.4 MB)
12274_2020_2685_MOESM4_ESM.pdf (5.8 MB)

References

[1]
Jin, R. C.; Zeng, C. J.; Zhou, M.; Chen, Y. X. Atomically precise colloidal metal nanoclusters and nanoparticles: Fundamentals and opportunities. Chem. Rev. 2016, 116, 10346-10413.
Crossref Google Scholar
[2]
Chakraborty, I.; Pradeep, T. Atomically precise clusters of noble metals: Emerging link between atoms and nanoparticles. Chem. Rev. 2017, 117, 8208-8271.
Crossref Google Scholar
[3]
Yan, J. Z.; Teo, B. K.; Zheng, N. F. Surface chemistry of atomically precise coinage-metal nanoclusters: From structural control to surface reactivity and catalysis. Acc. Chem. Res. 2018, 51, 3084-3093.
Crossref Google Scholar
[4]
Shang, L.; Azadfar, N.; Stockmar, F.; Send, W.; Trouillet, V.; Bruns, M.; Gerthsen, D.; Nienhaus, G. U. One-pot synthesis of near-infrared fluorescent gold clusters for cellular fluorescence lifetime imaging. Small 2011, 7, 2614-2620.
Crossref Google Scholar
[5]
Raut, S. L.; Fudala, R.; Rich, R.; Kokate, R. A.; Chib, R.; Gryczynski, Z.; Gryczynski, I. Long lived BSA Au clusters as a time gated intensity imaging probe. Nanoscale 2014, 6, 2594-2597.
Crossref Google Scholar
[6]
Xie, J. P.; Zheng, Y. G.; Ying, J. Y. Highly selective and ultrasensitive detection of Hg2+ based on fluorescence quenching of Au nanoclusters by Hg2+-Au+ interactions. Chem. Commun. 2010, 46, 961-963.
Crossref Google Scholar
[7]
Roy, S.; Palui, G.; Banerjee, A. The as-prepared gold cluster-based fluorescent sensor for the selective detection of AsIII ions in aqueous solution. Nanoscale 2012, 4, 2734-2740.
Crossref Google Scholar
[8]
Wang, Y.; Wan, X. K.; Ren, L. T.; Su, H. F.; Li, G.; Malola, S.; Lin, S. C.; Tang, Z. C.; Häkkinen, H.; Teo, B. K. et al. Atomically precise alkynyl-protected metal nanoclusters as a model catalyst: Observation of promoting effect of surface ligands on catalysis by metal nanoparticles. J. Am. Chem. Soc. 2016, 138, 3278-3281.
Crossref Google Scholar
[9]
Wan, X. K.; Wang, J. Q.; Nan, Z. A.; Wang, Q. M. Ligand effects in catalysis by atomically precise gold nanoclusters. Sci. Adv. 2017, 3, e1701823.
Crossref Google Scholar
[10]
Li, G.; Jin, R. C. Atomically precise gold nanoclusters as new model catalysts. Acc. Chem. Res. 2013, 46, 1749-1758.
Crossref Google Scholar
[11]
Yamazoe, S.; Koyasu, K.; Tsukuda, T. Nonscalable oxidation catalysis of gold clusters. Acc. Chem. Res. 2014, 47, 816-824.
Google Scholar
[12]
Zheng, K. Y.; Setyawati, M. I.; Leong, D. T.; Xie, J. P. Antimicrobial gold nanoclusters. ACS Nano 2017, 11, 6904-6910.
Google Scholar
[13]
Wang, Y. C.; Wang, Y.; Zhou, F. B.; Kim, P.; Xia, Y. N. Protein-protected Au clusters as a new class of nanoscale biosensor for label-free fluorescence detection of proteases. Small 2012, 8, 3769-3773.
Google Scholar
[14]
Konishi, K.; Iwasaki, M.; Shichibu, Y. Phosphine-ligated gold clusters with core+exo geometries: Unique properties and interactions at the ligand-cluster interface. Acc. Chem. Res. 2018, 51, 3125-3133.
Google Scholar
[15]
Tracy, J. B.; Crowe, M. C.; Parker, J. F.; Hampe, O.; Fields-Zinna, C. A.; Dass, A.; Murray, R. W. Electrospray ionization mass spectrometry of uniform and mixed monolayer nanoparticles: Au25[S(CH2)2Ph]18 and Au25[S(CH2)2Ph]18-x(SR)x. J. Am. Chem. Soc. 2007, 129, 16209-16215.
Google Scholar
[16]
Dass, A.; Stevenson, A.; Dubay, G. R.; Tracy, J. B.; Murray, R. W. Nanoparticle MALDI-TOF mass spectrometry without fragmentation: Au25(SCH2CH2Ph)18 and mixed monolayer Au25(SCH2CH2Ph)18-x(L)x. J. Am. Chem. Soc. 2008, 130, 5940-5946.
Google Scholar
[17]
Ren, L. T.; Yuan, P.; Su, H. F.; Malola, S.; Lin, S. C.; Tang, Z. C.; Teo, B. K.; Häkkinen, H.; Zheng, L. S.; Zheng, N. F. Bulky surface ligands promote surface reactivities of [Ag141X12(S-Adm)40]3+ (X = Cl, Br, I) nanoclusters: Models for multiple-twinned nanoparticles. J. Am. Chem. Soc. 2017, 139, 13288-13291.
Google Scholar
[18]
Gunawardene, P. N.; Corrigan, J. F.; Workentin, M. S. Golden opportunity: A clickable azide-functionalized [Au25(SR)18]- nanocluster platform for interfacial surface modifications. J. Am. Chem. Soc. 2019, 141, 11781-11785.
Google Scholar
[19]
Tang, Q.; Jiang, D. E. Comprehensive view of the ligand-gold interface from first principles. Chem. Mater. 2017, 29, 6908-6915.
Google Scholar
[20]
Muñoz-Castro, A. Potential of N-heterocyclic carbene derivatives from Au13(dppe)5Cl2 gold superatoms. Evaluation of electronic, optical and chiroptical properties from relativistic DFT. Inorg. Chem. Front. 2019, 6, 2349-2358.
Google Scholar
[21]
Narouz, M. R.; Osten, K. M.; Unsworth, P. J.; Man, R. W. Y.; Salorinne, K.; Takano, S.; Tomihara, R.; Kaappa, S.; Malola, S.; Dinh, C. T. et al. N-heterocyclic carbene-functionalized magic-number gold nanoclusters. Nat. Chem. 2019, 11, 419-425.
Google Scholar
[22]
Narouz, M. R.; Takano, S.; Lummis, P. A.; Levchenko, T. I.; Nazemi, A.; Kaappa, S.; Malola, S.; Yousefalizadeh, G.; Calhoun, L. A.; Stamplecoskie, K. G. et al. Robust, highly luminescent Au13 superatoms protected by N-heterocyclic carbenes. J. Am. Chem. Soc. 2019, 141, 14997-15002.
Google Scholar
[23]
Shen, H.; Deng, G. C.; Kaappa, S.; Tan, T. D.; Han, Y. Z.; Malola, S.; Lin, S. C.; Teo, B. K.; Häkkinen, H.; Zheng, N. F. Highly robust but surface-active: N-heterocyclic carbene-stabilized Au25 nanocluster. Angew. Chem., Int. Ed. 2019, 58, 17731-17735.
Google Scholar
[24]
Smith, C. A.; Narouz, M. R.; Lummis, P. A.; Singh, I.; Nazemi, A.; Li, C. H.; Crudden, C. M. N-Heterocyclic carbenes in materials chemistry. Chem. Rev. 2019, 119, 4986-5056.
Google Scholar
[25]
Zhukhovitskiy, A. V.; MacLeod, M. J.; Johnson, J. A. Carbene ligands in surface chemistry: From stabilization of discrete elemental allotropes to modification of nanoscale and bulk substrates. Chem. Rev. 2015, 115, 11503-11532.
Google Scholar
[26]
Mercs, L.; Albrecht, M. Beyond catalysis: N-Heterocyclic carbene complexes as components for medicinal, luminescent, and functional materials applications. Chem. Soc. Rev. 2010, 39, 1903-1912.
Google Scholar
[27]
Crudden, C. M.; Horton, J. H.; Ebralidze, I. I.; Zenkina, O. V.; McLean, A. B.; Drevniok, B.; She, Z.; Kraatz, H. B.; Mosey, N. J.; Seki, T. et al. Ultra stable self-assembled monolayers of N-heterocyclic carbenes on gold. Nat. Chem. 2014, 6, 409-414.
Google Scholar
[28]
Collado, A.; Gómez-Suárez, A.; Martin, A. R.; Slawin, A. M. Z.; Nolan, S. P. Straightforward synthesis of [Au(NHC)X] (NHC = N-heterocyclic carbene, X = Cl, Br, I) complexes. Chem. Commun. 2013, 49, 5541-5543.
Google Scholar
[29]
Walter, M.; Akola, J.; Lopez-Acevedo, O.; Jadzinsky, P. D.; Calero, G.; Ackerson, C. J.; Whetten, R. L.; Gronbeck, H.; Hakkinen, H. A unified view of ligand-protected gold clusters as superatom complexes. Proc. Natl. Acad. Sci. USA 2008, 105, 9157-9162.
Google Scholar
[30]
Gribble, G. W. Naturally occurring organohalogen compounds. Acc. Chem. Res. 1998, 31, 141-152.
Google Scholar
[31]
Petrone, D. A.; Ye, J. T.; Lautens, M. Modern transition-metal-catalyzed carbon-halogen bond formation. Chem. Rev. 2016, 116, 8003-8104.
Google Scholar
Nano Research
Volume 13 Issue 7,
July 2020
Pages 1908-1911
DOI: 10.1007/s12274-020-2685-0
Cite this article:
Shen H, Xiang S, Xu Z, et al. Superatomic Au13 clusters ligated by different N-heterocyclic carbenes and their ligand-dependent catalysis, photoluminescence, and proton sensitivity. Nano Research, 2020, 13(7): 1908-1911. https://doi.org/10.1007/s12274-020-2685-0
Topics:
Catalysis Catalyst activityGold nanoclusters LuminescenceNanoclustersOrganic compoundspH sensors
Part of a topical collection:
Sixth Nano Research Award

803

Views

97

Crossref

N/A

Web of Science

93

Scopus

7

CSCD

Altmetrics
Received: 10 November 2019
Revised: 26 January 2020
Accepted: 27 January 2020
Published: 29 February 2020
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
Return