Pyrrole derivatives have been shown to be completely or partially oxidized within the expandable channels of the 3D-coordination polymers [(R3Sn)(3)Fe(CN)(6)] (n) and [(R3Sn)(R (3) (') Sn)(2)Fe(CN)(6)] (n) , R and R' = Me, n-Bu, or Ph, to give novel class of supramolecular host-guest systems. The structures and physical properties of these host-guest systems depend on the reaction time, nature of the host and guest, the space empty within the network of the 3D-coordination polymers. Pyrrole undergoes oxidative polymerization in the channels of the 3D-coordination polymers to form semiconducting diamagnetic supramolecular host-guest systems. Whereas N-methylpyrrole and 2,5-dimethylpyrrole are not polymerized under these experimental conditions, but give paramagnetic charge transfer (CT) supramolecular host-guest systems.