A Near‐Infrared‐Emissive Alkynyl‐Protected Au<sub>24</sub> Nanocluster

Wan, Xian Kai; Xu, Wen; Yuan, Shang Fu; Gao, Yi; Zeng, Xiao Cheng; Wang, Quan Ming

doi:10.1002/anie.201503893

Cited by 163 publications

(119 citation statements)

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“…A grand challenge to scientists in this field, however, is the precise determination of atomic structures of liganded gold clusters. To date, atomic structures of tens of liganded gold clusters have been determined via X-ray crystallography56789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960616263. Nevertheless, these revelations appear serendipitous as the structural determination largely hinges on availability of single crystals for the liganded gold clusters.…”

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confidence: 99%

A grand unified model for liganded gold clusters

et al. 2016

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A grand unified model (GUM) is developed to achieve fundamental understanding of rich structures of all 71 liganded gold clusters reported to date. Inspired by the quark model by which composite particles (for example, protons and neutrons) are formed by combining three quarks (or flavours), here gold atoms are assigned three ‘flavours' (namely, bottom, middle and top) to represent three possible valence states. The ‘composite particles' in GUM are categorized into two groups: variants of triangular elementary block Au3(2e) and tetrahedral elementary block Au4(2e), all satisfying the duet rule (2e) of the valence shell, akin to the octet rule in general chemistry. The elementary blocks, when packed together, form the cores of liganded gold clusters. With the GUM, structures of 71 liganded gold clusters and their growth mechanism can be deciphered altogether. Although GUM is a predictive heuristic and may not be necessarily reflective of the actual electronic structure, several highly stable liganded gold clusters are predicted, thereby offering GUM-guided synthesis of liganded gold clusters by design.

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confidence: 99%

A grand unified model for liganded gold clusters

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“…Similar staples have also been found in the alkynylprotected Au 19 , [ 24 ] Au 23 , [ 25 ] and Au 24 . [ 26 ] On the other hand, phosphine-protected AuNCs tend to have simpler interfaces with well-defi ned cores and ligand layers, [27][28][29][30][31] …”

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Polymorphism of Phosphine-Protected Gold Nanoclusters: Synthesis and Characterization of a New 22-Gold-Atom Cluster

Zhang

Williard

Wang

2016

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A new Au22 nanocluster, protected by bis(2-diphenyl-phosphino)ethyl ether (dppee or C28 H28 OP2 ) ligand, has been synthsized and purified with high yield. Electrospray mass spectrometry shows that the new cluster has a formula of Au22 (dppee)7 , containing 22 gold atoms and seven dppee ligands. The cluster is found to be stable as a solid, but metastable in solution. The new cluster has been characterized by UV-Vis-NIR absorption spectroscopy, collision-induced dissociation, and (31) P-NMR. The properties of the new cluster have been compared with the previous Au22 (dppo)6 nanocluster (dppo = 1,8-bis(diphenyl-phosphino)octane or C32 H36 P2 ), which contains two fused Au11 units. All the experimental data indicate that the new Au22 (dppee)7 cluster is different from the previously known Au22 (dppo)6 cluster and represents a new Au22 core, which contains most likely one Au11 motif with several Au2 (dppee) or Au(dppee) units. The Au22 (dppee)7 cluster provides a new example of the ligand effects on the nuclearity and structural polymorphism of phosphine-protected atom-precise gold nanoclusters.

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“…For example, because there is an Au 13 core in Au 25 (SR) 18 with an Au/S ratio of 1.38, the Au x core is never smaller than Au 13 in Au n (SR) m with a larger Au/S ratio than 1.38. [32][33][34][35][36][51][52][53] Similarly, we try to find stable Au 13-16 clusters with a high symmetry as possible cores for the most stable atomic structure of Au 24 (Cys-Cys) 8 . Until now, all of the experimental and theoretical assessments have shown that the Au x core always has a high symmetry for the most stable ligand protected AuNC.…”

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Atomic structure of a peptide coated gold nanocluster identified using theoretical and experimental studies

Wang

Gao

et al. 2016

Nanoscale

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Peptide coated gold nanoclusters (AuNCs) have a precise molecular formula and atomic structure, which are critical for their unique applications in targeting specific proteins either for protein analysis or drug design. To date, a study of the crystal structure of peptide coated AuNCs is absent primarily due to the difficulty of obtaining their crystalline phases in an experiment. Here we study a typical peptide coated AuNC (Au24Peptide8, Peptide = H2N-CCYKKKKQAGDV-COOH, Anal. Chem., 2015, 87, 2546) to figure out its atomic structure and electronic structure using a theoretical method for the first time. In this work, we identify the explicit configuration of the essential structure of Au24Peptide8, Au24(Cys-Cys)8, using density functional theory (DFT) computations and optical spectroscopic experiments, where Cys denotes cysteine without H bonded to S. As the first multidentate ligand binding AuNC, Au24(Cys-Cys)8 is characterized as a distorted Au13 core with Oh symmetry covered by two Au(Cys-Cys) and three Au3(Cys-Cys)2 staple motifs in its atomic structure. The most stable configuration of Au24(Cys-Cys)8 is confirmed by comparing its UV-vis absorption spectrum from time-dependent density-functional theory (TDDFT) calculations with optical absorption measurements, and these results are consistent with each other. Furthermore, we carry out frontier molecular orbital (FMO) calculations to elucidate that the electronic structure of Au24(Cys-Cys)8 is different from that of Au24(SR)20 as they have a different Au/S ratio, where SR represents alkylthiolate. Importantly, the different ligand coatings, Cys-Cys and SR, in Au24(Cys-Cys)8 and Au24(SR)20 cause the different Au/S ratios in the coated Au24. The reason is that the Au/S ratio is crucial in determining the size of the Au core of the ligand protected AuNC, and the size of the Au core corresponds to a specific electronic structure. By the adjustment of ligand coatings from alkylthiolate to peptide, the Au/S ratio could be controlled to generate different AuNCs with versatile electronic structures, optical properties and reaction stabilities. Therefore, we propose a universal approach to obtain a specific Au/S ratio of ligand coated AuNCs by adjusting the ligand composition, thus controlling the chemicophysical properties of AuNCs with ultimately the same number of Au atoms.

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A Near‐Infrared‐Emissive Alkynyl‐Protected Au₂₄ Nanocluster

Cited by 163 publications

References 46 publications

A grand unified model for liganded gold clusters

A grand unified model for liganded gold clusters

Polymorphism of Phosphine-Protected Gold Nanoclusters: Synthesis and Characterization of a New 22-Gold-Atom Cluster

Atomic structure of a peptide coated gold nanocluster identified using theoretical and experimental studies

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A Near‐Infrared‐Emissive Alkynyl‐Protected Au24 Nanocluster

Cited by 163 publications

References 46 publications

A grand unified model for liganded gold clusters

A grand unified model for liganded gold clusters

Polymorphism of Phosphine-Protected Gold Nanoclusters: Synthesis and Characterization of a New 22-Gold-Atom Cluster

Atomic structure of a peptide coated gold nanocluster identified using theoretical and experimental studies

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A Near‐Infrared‐Emissive Alkynyl‐Protected Au₂₄ Nanocluster