Formation of polyrotaxane crystals driven by dative boron–nitrogen bonds

The integration of mechanically interlocked molecules (MIMs) into purely organic crystalline materials is expected to produce materials with properties that are not accessible using more classic approaches. To date, this integration has proved elusive. We present a dative boron-nitrogen bond-driven self-assembly strategy that allows for the preparation of polyrotaxane crystals. The polyrotaxane nature of the crystalline material was confirmed by both single-crystal x-ray diffraction analysis and cryogenic high-resolution low-dose transmission electron microscopy. Enhanced softness and greater elasticity are seen for the polyrotaxane crystals than for nonrotaxane polymer controls. This finding is rationalized in terms of the synergetic microscopic motion of the rotaxane subunits. The present work thus highlights the benefits of integrating MIMs into crystalline materials.