Interpenetrating Coordination Polymers from CuI or AgI and Flexible Ligands: 2D Polyrotaxanes and Interpenetrating Grids

The reaction of [Cu(CH3CN)4]NO3 or AgNO3 with flexible ligands 1,4‐bis(4‐pyridylmethyl)‐2,3,5,6‐tetrafluorobenzene (bpf) or 4,4′‐bis(4‐pyridylmethyl)‐2,2′,3,3′,5,5′,6,6′‐octafluorobiphenyl (bpfb) afforded two types of interpenetrating coordination polymers. The structures of [Cu2(bpf)3(NO3)2]n and [Ag2(bpf)3‐(NO3)2]n are 2D polyrotaxane networks in which 1D polymeric chains are aligned in a grid. The structure of {[Cu(bpfb)2]NO3}n is a 2D grid polymer with two‐fold parallel interpenetration. A fine weave: CuI/AgI and flexible bidentate ligands form two types of 2D polymers. The polyrotaxane is composed of rod‐and‐ring 1D chains that align in a grid, with rotaxane interactions at the intersections. The interpenetrating grid is an extremely twisted framework with twofold parallel interpenetration.