title: Time-resolved assembly of cluster-in-cluster {Ag₁₂}-in-{W₇₆} polyoxometalates under supramolecular control.
abstract: We report the time-resolved supramolecular assembly of a series of nanoscale polyoxometalate clusters (from the same one-pot reaction) of the form: [H(10+m)Ag18Cl(Te3W38O134)2]n, where n=1 and m=0 for compound 1 (after 4 days), n=2 and m=3 for compound 2 (after 10 days), and n=∞ and m=5 for compound 3 (after 14 days). The reaction is based upon the self-organization of two {Te3W38} units around a single chloride template and the formation of a {Ag12} cluster, giving a {Ag12}-in-{W76} cluster-in-cluster in compound 1, which further aggregates to cluster compounds 2 and 3 by supramolecular Ag-POM interactions. The proposed mechanism for the formation of the clusters has been studied by ESI-MS. Further, control experiments demonstrate the crucial role that TeO3(2-), Cl(-), and Ag(+) play in the self-assembly of compounds 1-3.
authors.affiliation: WestCHEM, School of Chemistry, The University of Glasgow, University Avenue, Glasgow G12 8QQ, Scotland (UK) http://www.croninlab.com.
authors.forename: Caihong
authors.initials: C
authors.lastname: Zhan
authors.forename: Jamie M
authors.initials: JM
authors.lastname: Cameron
authors.forename: Jing
authors.initials: J
authors.lastname: Gao
authors.forename: Jamie W
authors.initials: JW
authors.lastname: Purcell
authors.forename: De-Liang
authors.initials: DL
authors.lastname: Long
authors.forename: Leroy
authors.initials: L
authors.lastname: Cronin
keywords: cluster compounds; nanostructures; polyoxometalates; self-assembly; supramolecular chemistry