科研之友
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摘要
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@Ag-42( PhC/C)(34)(CF3COO)(2)] center dot CF3COO} ( 1), {(NH4)[(CrO4)(2)Cl@Ag-42(PhC/C)(34)(CrO4)( H2O)(2)] center dot 2BF(4) center dot CH3OH} n ( 2), [(CrO4)@ Ag-22(PhC/C)(16)(CF3SO3)(4)] (n) (3), and {[(CrO4)(2)@Ag-31(PhC/C) (22)(CF3SO3)(4)] center dot CF3SO3 center dot 2CH(3)OH center dot 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 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 Ag-18 and double CrO42- 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.
