In situ redox reactions facilitate the assembly of a mixed-valence metal-organic nanocapsule

• Published in: Nature communications Vol. 9; no. 1; pp. 2119 - 6
• Main Authors: Rathnayake, Asanka S., Fraser, Hector W. L., Brechin, Euan K., Dalgarno, Scott J., Baumeister, Jakob E., White, Joshua, Rungthanaphatsophon, Pokpong, Walensky, Justin R., Barnes, Charles L., Teat, Simon J., Atwood, Jerry L.
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 29.05.2018; Nature Publishing Group; Nature Portfolio
• Subjects: 639/638/541/965; 639/638/541/966; Aromatic compounds; Chemical synthesis; Electrochemistry; Humanities and Social Sciences; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Magnetic properties; Manganese; Manganese ions; Metal ions; Metals; multidisciplinary; Redox reactions; Science; Science (multidisciplinary); Self-assembly
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-018-04541-w

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 Mn II /Mn III -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. New approaches are required to access metal-organic assemblies with unusual structural properties. Here, the authors use an in situ redox reaction to obtain a mixed-valence, Mn(II)/Mn(III)-containing metal-organic nanocapsule with an odd number of metal ions.