Influence of Rotator Design on the Speed of Self-Assembled Four-Component Nanorotors: Coordinative Versus Dispersive Interactions

Inorganic Chemistry
Pronay Kumar BiswasMichael Schmittel

Abstract

Four-component nanorotors are prepared by the self-assembly of stator [Cu4(4)]4+with its four copper(I)-loaded phenanthroline stations and various rotators carrying one, two, or three pyridine terminals. The fourth component, 1,4-diazabicyclo[2.2.2]octane, serves as a connecting axle between rotator and stator. Capitalizing on the heteroleptic pyridyl and phenanthroline metal complexes concept, the rotator's pyridine terminals are connected to the copper(I)-loaded phenanthroline stations (Npy→ [Cu(phen)]+) in the STOP state and disconnected in the transition state of rotation. As the barrier of the thermally activated rotation, measured by variable-temperature1H NMR, is mainly governed by attractive forces between stator stations and rotator terminals, it increases along the series Ea(monopyridine rotator) < Ea(dipyridine rotator) < Ea(tripyridine rotator). However, there are even distinct differences in rate between rotors with equal number of rotator terminals. The change from the 5,10-dipyridyl (cis) to 5,15-dipyridyl (trans) zinc porphyrin rotator enhances the rotational frequency by almost 1000-fold. Density functional theory computational results suggest that not only coordinative Npy→ [Cu(phen)]+interactions but also dis...Continue Reading

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Citations

Mar 21, 2018·Chemical Communications : Chem Comm·Abir GoswamiMichael Schmittel
Jun 8, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Merve S ÖzerMichael Schmittel

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