Quantifying the barrier for the movement of cyclobis(paraquat-p-phenylene) over the dication of monopyrrolotetrathiafulvalene

Abstract

A bistable [2]pseudorotaxane 1⊂CBPQT·4PF₆ and a bistable [2]rotaxane 2·4PF₆ have been synthesised to measure the height of an electrostatic barrier produced by double molecular oxidation (0 to +2). Both systems have monopyrrolotetrathiafulvalene (MPTTF) and oxyphenylene (OP) as stations for cyclobis(paraquat-p-phenylene) (CBPQT⁴⁺). They have a large stopper at one end while the second stopper in 2⁴⁺ is composed of a thioethyl (SEt) group and a thiodiethyleneglycol (TDEG) substituent, whereas in 1⊂CBPQT⁴⁺, the SEt group has been replaced with a less bulky thiomethyl (SMe) group. This seemingly small difference in the substituents on the MPTTF unit leads to profound changes when comparing the physical properties of the two systems allowing for the first measurement of the deslipping of the CBPQT⁴⁺ ring over an MPTTF²⁺ unit in the [2]pseudorotaxane. Cyclic voltammetry and ¹H NMR spectroscopy were used to investigate the switching mechanism for 1⊂CBPQT·MPTTF⁴⁺ and 2·MPTTF⁴⁺, and it was found that CBPQT⁴⁺ moves first to the OP station producing 1⊂CBPQT·OP⁶⁺ and 2·OP⁶⁺, respectively, upon oxidation of the MPTTF unit. The kinetics of the complexation/decomplexation process occurring in 1⊂CBPQT·MPTTF⁴⁺ and in 1⊂CBPQT·OP⁶⁺ were studied, allowing the free energy of the transition state when CBPQT⁴⁺ moves across a neutral MPTTF unit (17.0 kcal mol⁻¹) or a di-oxidised MPTTF²⁺ unit (24.0 kcal mol⁻¹) to be determined. These results demonstrate that oxidation of the MPTTF unit to MPTTF²⁺ increases the energy barrier that the CBPQT⁴⁺ ring must overcome for decomplexation to occur by 7.0 kcal mol⁻¹.