Nanocluster Formation and Stabilization Fundamental Studies: Ranking the Nanocluster Stabilizing Ability of Halides
Abstract:Following a brief introduction to the nanocluster stabilization literature and DLVO (Derjaugin-Landau-Verwey-Overbeek) theory of colloidal stability, F−, Cl−, Br−, and I− are evaluated for their efficacy in the formation and stabilization of prototype Ir(0)n nanoclusters prepared from a [(1,5-COD)Ir(CH3CN)2][BF4] precursor in both acetone and propylene carbonate solvent. First, under conditions utilized previously for establishing an anion stabilization series ("Standard Conditions," 1.2 mM Ir precursor concentration at 22 °C in acetone solvent), the 5 criteria developed in 2002 for ranking nanocluster stabilizers are evaluated for each halide (each with 1 equiv BF−4 present from the Ir precursor). Under Standard Conditions, bulk metal is the final product (i.e., no stable nanoclusters) in the presence of each of the four halides, as well as for BF−4 in the absence of any halide. Next, each halide, again in the presence of 1 equiv BF−4 is evaluated under "Improved Conditions" (0.24 mM Ir precursor concentration at 60 °C in propylene carbonate solvent), propylene carbonate being known to be a preferred nanocluster solvent in the presence of anionic (electrostatic) stabilizers. Nanocluster syntheses under the Improved Conditions did, as expected, yield Ir(0)n nanoclusters for each of the four halide plus BF−4 systems as well as BF−4 alone, although none of these nanoclusters are isolable from solution. Importantly, even the traditionally weakly coordinating BF − 4is shown to contribute significantly to nanocluster stability in the high dielectric constant solvent propylene carbonate. Hence, the importance of anions in conjunction with a high dielectric constant solvent for nanocluster formation and stabilization is illustrated.
Document Type: Research Article
Publication date: 2007-07-01
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