The synthesis and single-crystal X-ray diffraction structure of a dimeric zinc-seamed nanocapsule using a mixed pyrogallol/resorcinol[4]arene are presented. The use of "mixed" macrocycles results in an incomplete seam of coordination bonds around the nanocapsule's typically octa-metalated belt. The self-assembly of the nanocapsule occurs such that the single resorcinol moiety of each macrocycle aligns transversely. This yields a hepta-metalated capsule where the defect occurs in such a way as to provide minimal disruption to the overall structure of the nanocapsule.
C-alkylpyrogallol[4]arenes (PgCs) have been studied for their ability to form metal-organic nanocapsules (MONCs) through coordination to appropriate metal ions. Here we present the synthesis and characterization of an MnII/MnIII-seamed MONC in addition to its electrochemical and magnetic behavior. This MONC assembles from 24 manganese ions and 6 PgCs, while an additional metal ion is located on the capsule interior, anchored through the introduction of bridging nitrite ions. The latter originate from an in situ redox reaction that occurs during the self-assembly process, thus representing a new route to otherwise unobtainable nanocapsules.
The synthesis and X-ray crystallographic
structure of the first
cobalt-seamed hexameric nanocapsule, [Co24(C-pentylpyrogallol[4]arene)6], is presented. The overall
metal–ligand arrangement of this novel capsule is similar to
that of previously reported copper- and nickel-seamed hexameric nanocapsules.
However, the title nanocapsule encloses a larger void space than those
found in previous hexameric nanocapsules.
Under suitable conditions, C-alkylpyrogallol[4]arenes (PgCs) arrange into spherical metal-organic nanocapsules (MONCs) upon coordination to appropriate metal ions. Herein we present the synthesis and structural characterization of a novel Fe II /Fe III-seamed MONC, as well as studies related to its electrochemical and magnetic behaviors. Unlike other MONCs which are assembled through 24 metal ions, this nanocapsule comprises 32 Fe ions, uncovering 8 additional coordination sites situated between the constituent PgC sub-units. The Fe II ions are likely formed by the reducing ability of DMF used in the synthesis, representing a novel synthetic route towards polynuclear mixed-valence MONCs.
Two structurally analogous Mn-seamed C-alkylpyrogallol[4]arene (PgC )-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 Mn ions, while the other is a mixed-valence Mn/ Mn 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).
A metal−organic nanocapsule consisting of 24 Zn 2+ ions and six pyrogallol[4]arene units has been synthesized and structurally characterized. All the Zn 2+ ions seaming the nanocapsule are disordered over two positions forming concave distortions on the framework.
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