Anion‐Templated Nanosized Silver Alkynyl Clusters: Cluster Engineering and Solution Behavior

Assembly of nanosized polynuclear metal clusters from simple building blocks usually involves complicated self‐organization processes and thus is a long‐standing challenge. Here, we demonstrate the controllable assembly, single‐crystal structures and solution behaviors of four molecular assemblies based on nanosized silver alkynyl clusters, formulated as {[(CrO 4 ) 2 Cl@Ag 42 (PhC≡C) 34 (CF 3 COO) 2 ]⋅CF 3 COO} ( 1 ), {(NH 4 )[(CrO 4 ) 2 Cl@Ag 42 (PhC≡C) 34 (CrO 4 )(H 2 O) 2 ]⋅2BF 4 ⋅CH 3 OH} n ( 2 ), [(CrO 4 )@Ag 22 (PhC≡C) 16 (CF 3 SO 3 ) 4 ] n ( 3 ), and {[(CrO 4 ) 2 @Ag 31 (PhC≡C) 22 (CF 3 SO 3 ) 4 ]⋅CF 3 SO 3 ⋅2CH 3 OH⋅H 2 O} n ( 4 ). In the presence of concomitant CrO 4 2− and Cl − templates, we could isolate a discrete cluster 1 and a polymeric chain‐like compound 2 by using different silver salts. Both 1 and 2 have a similar 42‐metallic cage, which traps two CrO 4 2− and one Cl − as anion templates. Using sole CrO 4 2− template, 3 and 4 were simultaneously isolated in a one‐pot reaction. Both of them are 1D chain structures based on single CrO 4 2− templated Ag 18 and double CrO 4 2− templated Ag 30 clusters, respectively. HR‐ESI‐MS was used to study the solution behaviors of 1 – 4 . This work has the following purposes: i) it presents the cluster engineering concept used in the assembly of polynuclear silver alkynyl clusters; ii) it exemplifies template effects from hetero and homo anions; and iii) it provides a controllable way to achieve assembly of silver alkynyl clusters.