Oxidation State Distributions Provide Insight into Parameters Directing the Assembly of Metal-Organic Nanocapsules.
Asanka S RathnayakeHector W L FraserEuan K BrechinScott J DalgarnoJakob E BaumeisterPokpong RungthanaphatsophonJustin R WalenskyCharles L BarnesJerry L AtwoodPublished in: Journal of the American Chemical Society (2018)
Two structurally analogous Mn-seamed C-alkylpyrogallol[4]arene (PgC n)-based metal-organic nanocapsules (MONCs) have been synthesized under similar reaction conditions and characterized by crystallographic, electrochemical, and magnetic susceptibility techniques. Both MONCs contain 24 Mn centers, but, somewhat surprisingly, marked differences in oxidation state distribution are observed upon analysis. One MONC contains exclusively MnII ions, while the other is a mixed-valence MnII/ MnIII assembly. We propose that these disparate oxidation state distributions arise from slight differences in pH achieved during synthesis, a factor that may lead to many spectacular new MONCs (and associated host-guest chemistries).