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Silver(I) Double and Multiple Salts Containing the 1,3‐Butadiynediide Dianion: Coordination Diversity and Assembly with the Supramolecular Synthon Ag 4 ⊂CCCC⊃Ag 4
Author(s) -
Zhao Liang,
Du Miao,
Mak Thomas C. W.
Publication year - 2007
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200700193
Subject(s) - synthon , chemistry , supramolecular chemistry , moiety , triple bond , crystallography , salt (chemistry) , stereochemistry , supramolecular assembly , coordination complex , metal , double bond , medicinal chemistry , polymer chemistry , crystal structure , organic chemistry
A series of 13 silver(I) double and multiple salts containing 1,3‐butadiynediide, C 4 2− , were synthesized by dissolving the silver carbide Ag 2 C 4 in a concentrated aqueous solution of one or more of the silver salts AgNO 3 , AgCF 3 CO 2 , AgC 2 F 5 CO 2 , AgF, AgBF 4 , and AgPF 6 . The 1,3‐butadiynediide anion invariably adopts a μ 4 ,μ 4 coordination mode in these compounds, which indicates that the Ag 4 ⊂CCCC⊃Ag 4 moiety can be used as a new type of metalloligand supramolecular synthon for the construction of coordination networks. Fine‐tuning with various ancillary anionic ligands caused the Ag 4 aggregate at each ethynide terminus to adopt a butterfly‐shaped, planar, or barblike configuration, within which the silver–ethynide interactions can be classified into three types: σ, π, and mixed (σ,π). The effect of coexisting nitrile ligands and quaternary ammonium salts on supramolecular assembly with the above synthon was also explored. The hydrolysis of PF 6 − and BF 4 − led to the formation of the quadruple salt Ag 2 C 4 ⋅4 AgNO 3 ⋅AgPF 2 O 2 ⋅Ag 3 PO 4 and a novel (F) 2 (H 2 O) 18 hydrogen‐bonded tape in the triple salt Ag 2 C 4 ⋅2 AgF⋅ 10 AgC 2 F 5 CO 2 ⋅CH 3 CN⋅12 H 2 O, respectively. The largest silver–ethynide cluster aggregate described to date, (C 4 ) 3 @Ag 18 , occurs in 3 Ag 2 C 4 ⋅ 12 AgC 2 F 5 CO 2 ⋅5[(BnMe 3 N)C 2 F 5 CO 2 ]⋅ 4 H 2 O (Bn=benzyl).