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Basic [Au 25 (SCH 2 CH 2 Py) 18 ] − ⋅Na + Clusters: Synthesis, Layered Crystallographic Arrangement, and Unique Surface Protonation
Author(s) -
Huang Zhong,
Ishida Yohei,
Yonezawa Tetsu
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201908905
Subject(s) - protonation , crystallography , chemistry , moiety , nuclear magnetic resonance spectroscopy , spectroscopy , solubility , ligand (biochemistry) , crystal structure , single crystal , aqueous solution , x ray crystallography , stereochemistry , diffraction , ion , organic chemistry , biochemistry , receptor , physics , quantum mechanics , optics
The synthesis of high‐purity and high‐yield Au 25 clusters protected by the basic pyridyl ethanethiol (HSCH 2 CH 2 Py, 4‐PyET and 2‐PyET) is presented. Single‐crystal X‐ray diffraction of the [Au 25 (4‐PyET) 18 ] − ⋅Na + clusters has revealed a structure similar to that known for the phenyl ethanethiolate analogue, but with pyridyl‐N coordination to Na + , a more relaxed ligand shell, and a profoundly layered arrangement in the solid state. Because of the pendant Py moiety, the [Au 25 (PyET) 18 ] − clusters are endowed with unique (de)protonation equilibria, which has been characterized in detail by UV/Vis absorption and 1 H NMR spectroscopy. [Au 25 (PyET) 18 ] − clusters showed an unexpectedly H + ‐dependent solubility that is tunable in aqueous and organic solvents. The successful synthesis of the basic Py‐terminated thiolate‐protected Au 25 clusters paves the way to realize a new family of metalloid clusters possessing basic properties.