An Ultrastable 155‐Nuclei Silver Nanocluster Protected by Thiacalixarene and Cyclohexanethiol for Photothermal Conversion

Thiacalix[4]arenes have emerged as a family of macrocyclic ligands to protect metal nanoparticles, but it remains a great challenge to solve the mystery of their structures at the atomic level, especially for those larger than 2 nm. Here, we report the largest known mixed‐valence silver nanocluster...

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Bibliographic Details
Published in:Angewandte Chemie 2022-08, Vol.134 (31)
Main Authors: Wang, Zhi, Alkan, Fahri, Aikens, Christine M, Kurmoo, Mohamedally, Zhen‐Yi Zhang, Ke‐Peng Song, Chen‐Ho Tung, Sun, Di
Format: Article
Language:English
Subjects:
Aromatic compounds
Chemistry
Crystal structure
Cyclohexanethiol
Ligands
Nanoclusters
Nanoparticles
Photothermal conversion
Silver
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Summary:Thiacalix[4]arenes have emerged as a family of macrocyclic ligands to protect metal nanoparticles, but it remains a great challenge to solve the mystery of their structures at the atomic level, especially for those larger than 2 nm. Here, we report the largest known mixed‐valence silver nanocluster [Ag155(CyS)40(TC4A)5Cl2] (Ag155) protected by deprotonated cyclohexanethiol (CySH) and macrocyclic ligand p‐tert‐butylthiacalix[4]arene (H4TC4A). Its single‐crystal structure consists of a metallic core of four concentric shells, Ag13@Ag42@Ag30@Ag70, lined with a organic skin of 40CyS− and 5TC4A4− and 2Cl−. Ag155 manifests an unusual pseudo‐5‐fold symmetry dictated by the intrinsic metal atom packing and the regioselective distribution of mixed protective ligands. This work not only reveals a macrocyclic ligand effect on the formation of a large silver nanocluster, but also provides a new structural archetype for comprehensively perceiving their interface and metal kernel structures.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202206742