title: Anion-Templated Nanosized Silver Alkynyl Clusters: Cluster Engineering and Solution Behavior.
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)2Cl@Ag42(PhC≡C)34(CF3COO)2]⋅CF3COO} (1), {(NH4)[(CrO4)2Cl@Ag42(PhC≡C)34(CrO4)(H2O)2]⋅2BF4⋅CH3OH}n(2), [(CrO4)@Ag22(PhC≡C)16(CF3SO3)4]n(3), and {[(CrO4)2@Ag31(PhC≡C)22(CF3SO3)4]⋅CF3SO3⋅2CH3OH⋅H2O}n(4). In the presence of concomitant CrO42-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 CrO42-and one Cl-as anion templates. Using sole CrO42-template, 3 and 4 were simultaneously isolated in a one-pot reaction. Both of them are 1D chain structures based on single CrO42-templated Ag18and double CrO42-templated Ag30clusters, 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.
authors.affiliation: Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China.
authors.forename: Shan-Shan
authors.initials: SS
authors.lastname: Zhang
authors.affiliation: State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.
authors.forename: Hai-Feng
authors.initials: HF
authors.lastname: Su
authors.affiliation: Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China.
authors.forename: Zhi
authors.initials: Z
authors.lastname: Wang
authors.affiliation: College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, 266042, P. R. China.
authors.forename: Lina
authors.initials: L
authors.lastname: Wang
authors.affiliation: Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China.
authors.forename: Quan-Qin
authors.initials: QQ
authors.lastname: Zhao
authors.affiliation: Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China.
authors.forename: Chen-Ho
authors.initials: CH
authors.lastname: Tung
authors.affiliation: Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China.
authors.forename: Di
authors.identifier: http://orcid.org/0000-0001-5966-1207
authors.initials: D
authors.lastname: Sun
authors.affiliation: State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.
authors.forename: Lan-Sun
authors.initials: LS
authors.lastname: Zheng
keywords: anion template; cluster engineering; silver; solution behavior