Functionally Rigid and Degenerate Molecular Shuttles

The preparation and dynamic behavior of two functionally rigid and degenerate 2]rotaxanes ( 1⋅ 4 PF₆ and 2⋅ 4 PF₆) in which a π-electron deficient tetracationic cyclophane, cyclobis(paraquat-p-phenylene) (CBPQT⁴⁺) ring, shuttles back and forth between two π-electron-rich naphthalene (NP) stations by making the passage along an ethynyl-phenylene-(PH)-ethynyl or butadiyne rod, are described. The 2]rotaxanes were synthesized by using the clipping approach to template-directed synthesis, and were characterized by NMR spectroscopic and mass spectrometric analyses. ¹H NMR spectra of both 2]rotaxanes show evidence for the formation of mechanically interlocked structures, resulting in the upfield shifts of the resonances for key protons on the dumbbell-shaped components. In particular, the signals for the peri protons on the NP units in the dumbbell-shaped components experienced significant upfield shifts at low temperatures, just as has been observed in the flexible 2]rotaxanes. Interestingly, the resonances for the same protons did not exhibit a significant upfield shift at 298 K, but rather only a modest shift. This phenomenon arises from the much reduced binding of the ethynyl-NP unit compared to the 1,5-dioxy-NP unit. This effect, in turn, increases the shuttling rate when compared to the 1,5-dioxy-NP-based rotaxane systems investigated previously. The kinetic and thermodynamic data of the shuttling behavior of the CBPQT⁴⁺ ring between the NP units were obtained by variable-temperature NMR spectroscopy and using the coalescence method to calculate the free energies of activation (ΔG_c^≠) of 9.6 and 10.3 kcal mol⁻¹ for 1⋅ 4 PF₆ and 2⋅ 4 PF₆, respectively, probed by using the rotaxane's α-bipyridinium protons. The solid-state structure of the free dumbbell-shaped compound ( 3 ) shows the fully rigid ethynyl-PH-ethynyl linker with a length (8.1 Å) twice as long as that (3.8 Å) of the butadiyne linker. Full-atomistic simulations were carried out with the DREIDING force field (FF) to probe the degenerate molecular shuttling processes, and afforded shuttling energy barriers (ΔG^≠=10.4 kcal mol⁻¹ for 1⋅ 4 PF₆ and 2⋅ 4 PF₆) that are in good agreement with the experimental values (ΔG_c^≠=9.6 and 10.3 kcal mol⁻¹ for 1⋅ 4 PF₆ and 2⋅ 4 PF₆, respectively, probed by using their α-bipyridinium protons).