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Kinetically‐Locked Metallomacrocycle for Host‐Guest Chemistry with Bulky Anions

Von Wiley-VCH zur Verfügung gestellt

The molecular structure of a kinetically-locked metallomacrocycle composed of three Co3+ ions and three diphenylanthracene derivatives with two β-diketonates on both sides was determined by X-ray crystallographic analysis and NMR analysis. The inner volume of the nanocavity of the macrocycle was estimated to be greater than 300 Å3. A large anion, tetraphenylborate, is hosted by the nanocavity.


As a robust and large molecular receptor, a kinetically-locked trinuclear Co(III) macrocycle was synthesized with bis(β-diketone) ligands having large π-panels of 9,10-diphenylanthracene moieties via a combination of Co(II)-assisted self-assembly and subsequent oxidation of the metal centers. The X-ray structure revealed that the macrocycle had a discrete nanocavity of more than 300 Å3, which was surrounded by three anthracenyl panels in the middle. As the macrocycle has three cationic centres on each metal ion and a large cavity, it acts as a guest receptor for sodium tetraphenylborate. The binding constant was estimated to be 4.0×10−2 M−1 from 1H NMR titration experiments, whereas no interaction was observed between the macrocycle and potassium 1-adamantanecarboxylate.

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