Anion‐Templated Nanosized Silver Alkynyl Clusters: Cluster Engineering and Solution Behavior. Issue 14 (14th February 2017)

• Record Type: Journal Article
• Authors: Zhang, Shan‐Shan; Su, Hai‐Feng; Wang, Zhi; Wang, Lina; Zhao, Quan‐Qin; Tung, Chen‐Ho; Sun, Di; Zheng, Lan‐Sun
• Is Part Of: Chemistry. Volume 23:Issue 14(2017)
• Page Start: 3432
• Page End: 3437
• Publication Date: 2017-02-14
• Subjects: anion template -- cluster engineering -- silver -- solution behavior; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201605440
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: 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 {[(CrO4 )2 Cl@Ag42 (PhC≡C)34 (CF3 COO)2 ]⋅CF3 COO} (1 ), {(NH4 )[(CrO4 )2 Cl@Ag42 (PhC≡C)34 (CrO4 )(H2 O)2 ]⋅2BF4 ⋅CH3 OH} n (2 ), [(CrO4 )@Ag22 (PhC≡C)16 (CF3 SO3 )4 ] n (3 ), and {[(CrO4 )2 @Ag31 (PhC≡C)22 (CF3 SO3 )4 ]⋅CF3 SO3 ⋅2CH3 OH⋅H2 O} n (4 ). In the presence of concomitant CrO4 2− and Cl − templates, we could isolate a discrete cluster1 and a polymeric chain‐like compound2 by using different silver salts. Both1 and2 have a similar 42‐metallic cage, which traps two CrO4 2− and one Cl − as anion templates. Using sole CrO4 2− template, 3 and4 were simultaneously isolated in a one‐pot reaction. Both of them are 1D chain structures based on single CrO4 2− templated Ag18 and double CrO4 2− templated Ag30 clusters, respectively. HR‐ESI‐MS was used to study the solution behaviors of1 –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. Abstract : Steering the herd : Cluster engineering of nanosized silver alkynyl clusters was achieved by adjusting anion templates.