Silver(I) Double and Multiple Salts Containing the 1,3‐Butadiynediide Dianion: Coordination Diversity and Assembly with the Supramolecular Synthon Ag4⊂CC?CC⊃Ag4 |
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Authors: | Liang Zhao Miao Du Prof. Dr. Thomas C. W. Mak Prof. Dr. |
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Affiliation: | 1. Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, China, Fax: (+852)?260‐3‐5057;2. College of Chemistry and Life Science, Tianjin Normal University, Tianjin, China |
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Abstract: | A series of 13 silver(I) double and multiple salts containing 1,3‐butadiynediide, C42?, were synthesized by dissolving the silver carbide Ag2C4 in a concentrated aqueous solution of one or more of the silver salts AgNO3, AgCF3CO2, AgC2F5CO2, AgF, AgBF4, and AgPF6. The 1,3‐butadiynediide anion invariably adopts a μ4,μ4 coordination mode in these compounds, which indicates that the Ag4?C?C? C?C?Ag4 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 Ag4 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 PF6? and BF4? led to the formation of the quadruple salt Ag2C4?4 AgNO3?AgPF2O2?Ag3PO4 and a novel (F)2(H2O)18 hydrogen‐bonded tape in the triple salt Ag2C4?2 AgF? 10 AgC2F5CO2?CH3CN?12 H2O, respectively. The largest silver–ethynide cluster aggregate described to date, (C4)3@Ag18, occurs in 3 Ag2C4? 12 AgC2F5CO2?5[(BnMe3N)C2F5CO2]? 4 H2O (Bn=benzyl). |
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Keywords: | argentophilicity carbides coordination modes silver supramolecular synthons |
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