The hexapodal ligand hexakis(isonicotinoyl)cyclotricatechylene (L1) belonging to the cyclotriveratrylene family of host-molecules has been synthesised and used in the assembly of a series of coordination polymer materials with Re(I), Co(II), Cu(II), Ni(II) and Ag(I) salts. Single crystal structures of the coordination polymers [Re3(L1)2Br3(CO)3] 1, and an isomorphic [M3L2] series where M = Co, Cu or Ni, reveal 2D framework structures with a simplified topology of 36 or hxl. These are composed of M6(L1)2 metallo-cages linked together in a pair-wise fashion through each metal centre. Compound 1 is a rare example of a rhenium coordination polymer and was investigated for guest uptake from solution, complexing I2. The mixed-ligand species [Cu2(L1)(CF3CO2)3(isonicotinate)] forms a (3,4,5)-connected 2D coordination polymer, while [Ag2(L1)(DMF)2]·2BF4·2(H2O)·6(DMF) features a 2D network of (3,6)-connectivity and with kagome dual (kgd) topology.
