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Elimination‐Fusion Self‐Assembly of a Nanometer‐Scale 72‐Nucleus Silver Cluster Caging a Pair of [EuW 10 O 36 ] 9− Polyoxometalates
Author(s) -
Zhang ShanShan,
Su HaiFeng,
Wang Zhi,
Wang XingPo,
Chen WenXian,
Zhao QuanQin,
Tung ChenHo,
Sun Di,
Zheng LanSun
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201705264
Subject(s) - polyoxometalate , cluster (spacecraft) , electrospray ionization , crystallography , chemistry , ion , crystallization , single crystal , x ray photoelectron spectroscopy , mass spectrometry , analytical chemistry (journal) , physics , chromatography , organic chemistry , nuclear magnetic resonance , computer science , programming language , catalysis , biochemistry
The largest known polyoxometalate (POM)‐templated silver‐alkynyl cluster, [(EuW 10 O 36 ) 2 @Ag 72 ( t BuC≡C) 48 Cl 2 ⋅ 4 BF 4 ] ( SD/Ag20 ), was isolated under solvothermal conditions and structurally characterized. It was confirmed by single‐crystal X‐ray diffraction (SCXRD) as a {EuW 10 } 2 ‐in‐{Ag 72 } clusters‐in‐cluster rod‐like compound. The high‐resolution electrospray ionization mass spectrometry (HR‐ESI‐MS) shows that such a double anion‐templated cluster is assembled from a crucial single anion‐templated Ag 42 intermediate in the solution. The crystallization of Ag 42 species ( SD/Ag21) , followed by SCXRD, gave an important clue about the assembly route of SD/Ag20 in solution: the Ag 42 cluster eliminates six silver atoms laterally, then fuses together at the vacant face to form the final Ag 72 cluster (elimination‐fusion mechanism). The characteristic emission of [EuW 10 O 36 ] 9− is well maintained in SD/Ag20 . This work not only provides a new method for the synthesis of larger silver clusters as well as the functional integration of the silver cluster and POMs, but also gives deep insights about the high‐nuclear silver cluster assembly mechanism.