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 lacks controllability, thus is a challenge task for a long time. Here we demonstrate the controllable assembly, single crystal structures and solution behaviors of four molecular assemblies based on nanosized silver alkynyl clusters. In the presence of concomitant CrO42- and Cl- templates, we could isolated a discrete cluster 1 and a polymeric chain-like compound 2 based on similar [(CrO4)Cl@Ag42] cluster units by using different silver salts. Both 1 and 2 have a similar 42-metallic cage which traps two CrO42- and one Cl- as anion templates. Using sole CrO42- template, 3 and 4 were simultaneously isolated in one-pot reaction. Both of them are 1D chain structures based on single CrO42- templated Ag18 and double CrO42- templated Ag30 clusters, respectively. High-resolution electrospray mass spectrometry (HR-ESI-MS) was also used to study the solution behaviors of 1-4. This work i) presents the cluster engineering concept used in the assembly of polynuclear silver alkynyl clusters; ii) exemplifies template effects from hetero and homo anions; and iii) provides a controllable way to achieve assembly of silver alkynyl clusters.