Supramolecular Pseudorotaxane Polymers from Biscryptands and Bisparaquats

Five new bis(dibenzo-30-crown-10-based cryptand)s were synthesized, two of which ( 16 and 17 ) had long (12-atom), flexible spacers that led to cooperative complexation of dibenzyl paraquat TFSI ( K ave = 4.36 × 10 5 M –1 for 17•2b ). Self-assembly of 16 and 17 with bisparaquats with similar spacers ( 18, 21, and 23 ) led to high molecular weight supramolecular pseudorotaxane polymers in solution. Continuous, flexible fibers were drawn from concentrated solutions. 17 with C 10 -linked bisparaquat 23 in dichloromethane (DCM) produced a log–log viscosity vs concentration plot with a limiting slope of 3.55, confirming high molecular weight; at 37 mM, the degree of polymerization was estimated to be 126 and M n = 407 kDa. These are the first truly polymeric pseudorotaxane-type AA/BB supramolecular polymers.