Controlling Gold Nanoclusters by Diphospine Ligands

We report the synthesis and structure determination of a new Au22 nanocluster coordinated by six bidentate diphosphine ligands: 1,8-bis(diphenyl­phosphino) octane (L8 for short). Single crystal X-ray crystallography and electrospray ionization mass spectrometry show that the cluster assembly is neut...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2014-01, Vol.136 (1), p.92-95
Main Authors: Chen, Jing, Zhang, Qian-Fan, Bonaccorso, Timary A, Williard, Paul G, Wang, Lai-Sheng
Format: Article
Language:English
Subjects:
Crystallography, X-Ray
Gold - chemistry
Ligands
Mass Spectrometry
Metal Nanoparticles - chemistry
Models, Molecular
Phosphines - chemistry
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Summary:We report the synthesis and structure determination of a new Au22 nanocluster coordinated by six bidentate diphosphine ligands: 1,8-bis(diphenyl­phosphino) octane (L8 for short). Single crystal X-ray crystallography and electrospray ionization mass spectrometry show that the cluster assembly is neutral and can be formulated as Au22(L8)6. The Au22 core consists of two Au11 units clipped together by four L8 ligands, while the additional two ligands coordinate to each Au11 unit in a bidentate fashion. Eight gold atoms at the interface of the two Au11 units are not coordinated by any ligands. Four short gold–gold distances (2.64–2.65 Å) are observed at the interface of the two Au11 clusters as a result of the clamping force of the four clipping ligands and strong electronic interactions. The eight uncoordinated surface gold atoms in the Au22(L8)6 nanocluster are unprecedented in atom-precise gold nanoparticles and can be considered as potential in situ active sites for catalysis.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja411061e