title: Survival of the Fittest Nanojar: Stepwise Breakdown of Polydisperse Cu27-Cu31 Nanojar Mixtures into Monodisperse Cu27(CO3) and Cu31(SO4) Nanojars.
abstract: Nanojars are emerging as a class of anion sequestration agents of unparalleled efficiency. Dinegative oxoanions (e.g., carbonate, sulfate) template the formation of a series of homologous nanojars [Cu(OH)(pyrazolato)]n (n=27-31). Pyridine selectively transforms less stable, larger CO3(2-) nanojars (n=30, 31) into more stable, smaller ones (n=27, 29), but leaves all SO4(2-) nanojars (n=27-29, 31) intact. Ammonia, in turn, transforms all less stable nanojars into the most stable one and allows the isolation of pure [CO3(2-)⊂{Cu(OH)(pz)}27] and [SO4(2-)⊂{Cu(OH)(pz)}31]. A comprehensive picture of the solution and solid-state intricacies of nanojars was revealed by a combination of variable temperature NMR spectroscopy, tandem mass spectrometry, and X-ray crystallography.
authors.affiliation: Department of Chemistry, Western Michigan University, Kalamazoo, Michigan, 49008-5413, USA.
authors.forename: Basil M
authors.initials: BM
authors.lastname: Ahmed
authors.affiliation: Department of Chemistry, Western Michigan University, Kalamazoo, Michigan, 49008-5413, USA.
authors.forename: Blair R
authors.initials: BR
authors.lastname: Szymczyna
authors.affiliation: Department of Chemistry, Western Michigan University, Kalamazoo, Michigan, 49008-5413, USA.
authors.forename: Sarut
authors.initials: S
authors.lastname: Jianrattanasawat
authors.affiliation: Department of Chemistry, Western Michigan University, Kalamazoo, Michigan, 49008-5413, USA.
authors.forename: Stuart A
authors.initials: SA
authors.lastname: Surmann
authors.affiliation: Department of Chemistry, Western Michigan University, Kalamazoo, Michigan, 49008-5413, USA. gellert.mezei@wmich.edu.
authors.forename: Gellert
authors.identifier: http://orcid.org/0000-0002-3120-3084
authors.initials: G
authors.lastname: Mezei
keywords: NMR spectroscopy; anion encapsulation; copper; paramagnetism; pyrazolate complexes; self-assembly