Binuclear alkyne manganese carbonyls of the type (RC≡CR')Mn2(CO)
Quantifying the barrier for the movement of cyclobis(paraquat- p -phenylene) over the dication of monopyrrolotetrathiafulvalene
A bistable [2]pseudorotaxane 1⊂CBPQT·4PF 6 and a bistable [2]rotaxane 2·4PF 6 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) (CBPQT 4+ ). They have a large stopper at one end while the second stopper in 2 4+ is composed of a thioethyl (SEt) group and a thiodiethyleneglycol (TDEG) substituent, whereas in 1⊂CBPQT 4+ , 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 CBPQT 4+ ring over an MPTTF 2+ unit in the [2]pseudorotaxane. Cyclic voltammetry and 1 H NMR spectroscopy were used to investigate the switching mechanism for 1⊂CBPQT·MPTTF 4+ and 2·MPTTF 4+ , and it was found that CBPQT 4+ moves first to the OP station producing 1⊂CBPQT·OP 6+ and 2·OP 6+ , respectively, upon oxidation of the MPTTF unit. The kinetics of the complexation/decomplexation process occurring in 1⊂CBPQT·MPTTF 4+ and in 1⊂CBPQT·OP 6+ were studied, allowing the free energy of the transition state when CBPQT 4+ moves across a neutral MPTTF unit (17.0 kcal mol −1 ) or a di-oxidised MPTTF 2+ unit (24.0 kcal mol −1 ) to be determined. These results demonstrate that oxidation of the MPTTF unit to MPTTF 2+ increases the energy barrier that the CBPQT 4+ ring must overcome for decomplexation to occur by 7.0 kcal mol −1 .
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- Award ID(s):
- 2105848
- NSF-PAR ID:
- 10352727
- Date Published:
- Journal Name:
- Organic & Biomolecular Chemistry
- Volume:
- 20
- Issue:
- 11
- ISSN:
- 1477-0520
- Page Range / eLocation ID:
- 2233 to 2248
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d1ob02263f
