A new mixed-valent silver complex [AgII(tmc)][AgII(tmc)(H2O)]2·[AgI11(C2)(CF3CO2)12(H2O)4]2
(tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) was synthesized by adding tmc to a concentrated aqueous solution of silver trifluoroacetate containing dissolved silver acetylide. Single-crystal X-ray analysis revealed that the resulting [AgII(tmc)]2+ and [AgII(tmc)(H2O)]2+ complex cations induce the self-assembly of a centrosymmetric anionic cluster dimer from the Ag(I), C22− and CF3CO2− species. A new type of cluster core [C2@Ag8]Ag was observed, which takes the form of a bicapped trigonal prism with a pendant silver atom attached to one edge.
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