Double Rotors with Fluxional Axles: Domino Rotation and Azide-Alkyne Huisgen Cycloaddition Catalysis.

The simple preparation of the multicomponent devices [Cu4 (A)2 ]4+ and [Cu2 (A)(B)]2+ , both rotors with fluxional axles undergoing domino rotation, highlights the potential of self-sorting. The concept of domino rotation requires the interconversion of axle and rotator, allowing the spatiotemporal decoupling of two degenerate exchange processes in [Cu4 (A)2 ]4+ occurring at 142 kHz. Addition of two equiv of B to rotor [Cu4 (A)2 ]4+ afforded the heteromeric two-axle rotor [Cu2 (A)(B)]2+ with two distinct exchange processes (64.0 kHz and 0.55 Hz). The motion requiring a pyridine→zinc porphyrin bond cleavage is 1.2×105 times faster than that operating via a terpyridine→[Cu(phenAr2 )]+ rupture. Finally, both rotors are catalysts due to their copper(I) content. The fast domino rotor (142 kHz) was shown to suppress product inhibition in the catalysis of the azide-alkyne Huisgen cycloaddition.