Kinked-Helix Actinide Polyrotaxanes from Weakly Bound Pseudorotaxane Linkers with Variable Conformations.

Abstract

The incorporation of a mechanically interlocked molecule such as pseudorotaxane into metal-organic coordination polymers has afforded plenty of new hybrid materials with special structures and unique properties. In this work, we employ a weakly bound cucurbit[6]uril (CB[6])-bipyridinium pseudorotaxane as a supramolecular precursor to assemble with uranyl, aiming to construct uranyl-rotaxane coordination polymers (URCPs) with intriguing structures. By adjusting the synthetic conditions, a new kinked-helix uranyl rotaxane compound (URCP3), together with three other compounds URCP1, URCP2, and URCP4 varying from 1D chains to 2D interwoven networks, was obtained. Detailed structural analyses indicate that the pseudorotaxane ligand (C8BPCA@CB[6]) shows great configuration diversity in the construction of URCPs, which is most probably due to the weak binding strength between the host and guest molecules. Specifically, based on the monodentate coordination of the end carboxyl groups of C8BPCA forced by the surrounding unilaterally-chelated oxalate, the entire flexible pseudorotaxane linker will be more likely to undergo conformational change, thereby binding to the uranyl center from both sides of the uranyl equatorial plane and promoting the formation of a kinked helix structure of URCP3 that is shaped like a Chinese knot along [001]. This work enriches the library of actinide-rotaxane compounds and provides a new approach to construct metal-organic compounds with complicated structures using weakly bonded pseudorotaxanes as well.