Coordination polymers on the basis of the assembly of metal ion "connectors" and multidentate ligand "linkers" have been of great interest due to their intriguing architectures and versatile applications.1-9 Metallotetraazamacrocycles bearing equatorial amines coordinated to the central metal ions and axial sites opened for incoming "linkers" are good "connectors" as building blocks for the construction of coordination polymers.
10-15Among multidentate ligands, polycarboxylates have been widely used as "linkers" due to their versatile coordination modes toward metal ions. [16][17][18][19] An fdc (fdc = 1,1'-ferrocenedicarboxylate ion) ligand as a kind of polycarboxylates has attracted attention not only in the field of coordination chemistry but also in the field of organometallic chemistry. [20][21][22][23] During our efforts to explore the molecular interactions between metallomacrocycles and polycarboxylate ligands in zinc(II) and cadmium(II) tetraazamacrocycles containing bridging polycarboxylate ligands, we successfully synthesized and structurally characterized two 1D zinc(II) coordination polymers 1 and 2, where each ferrocenyl of bridging fdc ligands adopts different conformation, and a macrocyclic cadmium(II) dimer 3. Thus, two Cp (Cp = cyclopentadienyl) rings of fdc ligands in 1 are mutually staggered, whereas they are eclipsed in 2. The cadmium(II) cyclams with folded macrocycles are bridged by an oxalate ligand in 3. In this report we describe the details of the synthesis and structures of 1-3.