Four-component nanorotors are prepared by the self-assembly of stator [Cu(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 (N → [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-temperature H NMR, is mainly governed by attractive forces between stator stations and rotator terminals, it increases along the series E (monopyridine rotator) < E (dipyridine rotator) < E (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 N → [Cu(phen)] interactions but also dispersive attraction influence the barrier of rotation.
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