Several new first-row transition-metal complexes have been synthesised by combining the polynitrile dianion HCTMCP(2-) (hexacyanotrimethylenecyclopropandiide) with neutral, chelating co-ligands; 2,2'-bipyridine, 1,10-phenanthroline and 3-(2-pyridyl)pyrazole. The products cover a remarkable range of species including mononuclear complexes, dimers, charge-separated species and coordination polymers. Complexes containing 2,2'-bipyridine take the form [Mn(2,2'-bipy)(2)(HCTMCP)](2)·2MeOH (1) or [M(2,2'-bipy)(3)](HCTMCP) (2Fe and 2Co) which are dimeric and charge-separated products, respectively. The products obtained using 1,10-phenanthroline were the discrete complex [Co(HCTMCP)(1,10-phen)(2)(H(2)O)]·H(2)O·MeCN (3) and the 1D coordination polymer [Mn(HCTMCP)(1,10-phen)(H(2)O)(MeOH)] (4). Complexes using the 3-(2-pyridyl)pyrazole co-ligand (pypzH) form similar 1D complexes to 4, namely [Mn(pypzH)(HCTMCP)(MeOH)(H(2)O)] (5) and [M(pypzH)(HCTMCP)(MeOH)(2)] (6Co and 6Fe), albeit with different hydrogen-bonding motifs between the chains. The polymeric HCTMCP complexes show weak to zero antiferromagnetic coupling between metal centres and thus no long-range ordering.