Reversible Interconversion of a Static Metallosupramolecular Cage Assembly into a High-Speed Rotor: Stepless Adjustment of Rotational Exchange by Nucleophile Addition

Inorganic Chemistry
Suchismita SahaMichael Schmittel

Abstract

The self-assembled cage ROT-1 was prepared from the pyridine-terminated rotator 1, the phenanthroline-appended stator 2, DABCO, and copper(I) ions in a ratio of 1:1:1:4. This four-component assembly is held together by two pyridine→[Cu(phenAr2)]+ as well as two DABCO→zinc porphyrin interactions (phenAr2 = 2,9-diarylphenanthroline) and does not show any motion on the NMR time scale ( k < 0.1 s-1, 298 K). However, it is converted to the fast nanorotor ROT-1 xCD3CN by addition of CD3CN [ x = (v/v)% of acetonitrile in dichloromethane] due to acceleration of both pyridine→copper(I) dissociation steps. Now the rotator is able to visit all four copper(I)-loaded phenanthroline stations of the stator. Depending on the amount of CD3CN, the exchange frequency of the nanorotor varies from 0.7 s-1 (CD3CN:CD2Cl2 = 1:29) to 8000 s-1 (CD3CN:CD2Cl2 = 1:5) at 25 °C. When iodide (I-) is added to the static assembly ROT-1, the rotational speed increases even more drastically ( k = 20 000 s-1), again due to accelerating the rate-determining pyridine→copper(I) dissociation step. In both cases, a sigmoidal relationship is established between exchange frequency and the concentration of added nucleophile (CD3CN or iodide) that suggests the presence of ...Continue Reading

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Citations

Jun 8, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Merve S ÖzerMichael Schmittel
Apr 17, 2020·Chemistry : a European Journal·Matthias Hardy, Arne Lützen

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