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Johnson Solids: Anion‐Templated Silver Thiolate Clusters Capped by Sulfonate
Author(s) -
Wang Zhi,
Su HaiFeng,
Wang XingPo,
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.201704298
Subject(s) - crystallography , cluster (spacecraft) , chemistry , ion , template , sulfonate , crystal structure , trigonal crystal system , stereochemistry , materials science , sodium , nanotechnology , organic chemistry , computer science , programming language
Sulfonates were incorporated into six novel high‐nuclearity silver(I) thiolate clusters under the guidance of anion templates varied from S 2− , SO 4 2− , α‐[Mo 5 O 18 ] 6− , β‐[Mo 5 O 18 ] 6− , [Mo 2 O 8 ] 4− , to [Mo 4 O 14 (SO 4 )] 6− . Single crystal X‐ray analysis revealed that SD/Ag1 , SD/Ag3 , SD/Ag5 , and SD/Ag6 are discrete [S@Ag 60 ], [α‐Mo 5 O 18 @Ag 36 ], [Mo 2 O 8 @Ag 30 ] 2 , and [Mo 4 O 14 (SO 4 )@Ag 73 ] clusters, respectively, whereas SD/Ag2 and SD/Ag4 are one‐dimensional (1D) chains based on the [SO 4 @Ag 20 ] and [β‐Mo 5 O 18 @Ag 36 ] cluster subunits, respectively. Their silver skeletons are protected exteriorly by thiolates and sulfonates and interiorly supported by diverse anions as templates. Structurally, cluster SD/Ag1 is a typical core–shell structure comprised of an inner Ag 12 cuboctahedron and an outer Ag 48 shell. The sulfate‐templated drum‐like Ag 20 cluster subunits are bridged by PhSO 3 − to give a 1D chain of SD/Ag2 . Complex SD/Ag3 and SD/Ag4 are spindle‐like Ag 36 clusters with isomeric [Mo 5 O 18 ] 6− inside, and the latter is further extended to a 1D chain through PhSO 3 − bridges. A pair of [Mo 2 O 8 ] 4− templated gourd‐like Ag 30 clusters are dimerized in a head‐to‐head fashion to form SD/Ag5 . Complex SD/Ag6 is the largest cluster in this family and doubly templated by unprecedented [Mo 4 O 14 (SO 4 )] 6− anions. Geometrically, the silver shells of SD/Ag1 – SD/Ag5 show the polyhedral features of Johnson solids, instead of the usual Platonic or Archimedean solids. Solution behaviors and luminescent properties were also investigated in detail.