Eleven new coordination polymers, namely, [Zn(L-1)(bbi)]center dot 0.5H(2)O (1), [Co(L (1))(bbi)]center dot 0.5H(2)O (2), [Cd (L-1)(bbi)]center dot 0.5H(2)O (3), [Zn(L-2)(bbi)]center dot H2O (4), [Co(L-2)(bbi)]center dot 1.25H(2)O (5), [Cd(L-2)(bbi)(0.5)(H2O)] (6), [Zn (L-3)(bbi)]center dot H2O (7), [Co(L-3)(bbi)]center dot H2O (8), [Cd((L)3)(bbi)(0.5)(H2O)]center dot 2H(2)O (9), [Zn(HL4)(bbi)] (10) and [Cd(HL4)(bbi)(H2O)]center dot 1.5H(2)O (11), where H2L1 = 4-carboxy-phenylene-methyleneamino-2-benzyl acid, H2L2 = 4-carboxy-phenylene-methyleneamino-3-benzyl acid, H2L3 = 4-carboxy-phenylene-methyleneamino- 4-benzyl acid, H3L4 = 4-carboxy-phenylene-methyleneimino-3,5-dibenzyl acid and bbi 1,4-bis(1H-imidazol-1-yl) butane, have been synthesized under hydrothermal conditions. Compounds 1-3 are isomorphous, and show 2D two-fold interpenetrating 6(3)-hcb networks. Compound 5 is isomorphous with 4. Compound 4 displays a 2D undulated layer structure. Adjacent layers are connected through hydrogen bonds to generate a 3D supramolecular architecture. The structure of compound 6 is an unusual 2D 2-fold parallel interpenetrating network with both polyrotaxane and polycatenane characters. 7 and 8 show 2D undulated sheet structures. The sheets are penetrated by each other to give rise to 3D polycatenations. The structure of compound 9 is an intriguing 2D self-penetrating network. Further, the pi-pi interactions among the L-3 anions link the 2D networks into a 3D supramolecular assembly. Compound 10 displays a corrugated 2D (4,4) sheet with dangling arms. Each sheet is threaded by the dangling arms of two others, leading to an unusual 3D polythreading framework. The structure of compound 11 is a 3D (3,4)-connected framework with (4(2)center dot 6)(4(2)center dot 6 center dot 12(3)) topology. The thermogravimetric and luminescent properties have also been studied for the compounds.