Construction of 2D Interdigitated Polyrotaxane Layers and their Transformation to a 3D Polyrotaxane by a...

Following the pioneering work of Sauvage and Stoddart on rotaxanes, construction of higher dimensional polyrotaxanes in metal-organic frameworks (MOFs) via a modified protocol is challenging. We present the formation of a two-dimensional (2D) polyrotaxane and its conversion to a three-dimensional (3D) polyrotaxane MOF via a photoreaction between interdigitated "olefin wheels". For this purpose, a 2-fold entangled 2D MOF [Pb₂(bpp)(sdc)₂] (1), showing a 2D + 2D → 2D polyrotaxane motif, has been synthesized from the solvothermal reaction of lead(II) nitrate, 3,3'-stilbenedicarboxylic acid (H₂sdc) containing an olefin group, and 1,4-bis(4-pyridyl)piperazine (bpp). The single-crystal X-ray diffraction analysis of 1 revealed that the adjacent entangled 2D layers are interdigitated, with the separation of 3.72 Å between C═C bond pairs in adjacent layers satisfying Schmidt's criteria for the occurrence of a [2 + 2] photocycloaddition reaction. Irradiation of the single crystals of 1 under UV light resulted in formation of a 3D polyrotaxane, [Pb₂(bpp)(rctt-tccb)] (2), due to a [2 + 2] photocycloaddition reaction between two wheels via a single-crystal to single-crystal transformation. The photocycloaddition and partial thermal cleavage reaction between 1 and 2 were confirmed by ¹H NMR and powder X-ray diffraction (PXRD) in solution and the solid state, respectively. The present approach could contribute to the understanding of the construction of higher dimensional polyrotaxanes which are not accessible by the traditional routes.