Eleven new coordination polymers, [Zn-2(ctPY)(2)(HCOO)(2)](n)center dot 3nH(2)O (1), [Zn-2(ctPY)(2)(HCOO)(2)(H2O)](n)center dot nH(2)O (2), [Zn-2(ctPY)(2)(H2O)(4)](n)center dot 2n(CH3COO)center dot nH(2)O (3), [Zn-2(ctPY)(2)(CH3COO)(2)](n)center dot nH(2)O (4), [Zn(ctPY)(2)](n)center dot nH(2)O (5), [Zn-2(ctpy)(2)(Hidc)(H2O)(2)]n (6), [Cd-2(ctpy)(4)](n) (7), [Cd-2(ctpy)(2)(Hidc)](n) (8), [Co-2(ctpy)(2)(HCOO)(2)(H2O)(2)](n)center dot nH(2)O (9), [Co(ctpy)(DMF)(ox)(0.5)](n) (10), [Co(ctpy)(ox)(0.5)](n) (11) and the closely related compound [Zn(ctpy) (ox)(0.5)](n)center dot 0.5nH(2)O (12) (Hctpy = 4'-carboxy-4,2':6',4 ''-terpyridine, H(2)ox = oxalic acid and H(3)idc = imidazole-4,5-dicarboxylic acid) have been synthesized by hydro(solvo)thermal reaction of 4'-carboxy-4,2':6',4 ''-terpyridine with divalent metal salts and characterized by elemental analysis, IR spectra, single crystal X-ray diffraction. Compounds 1 and 4 have similar structure which demonstrate a two-fold interpenetrating 3D framework with a 3-connected utp topological net, which contains the same number of left and right-handed 2(1) helical chains. Compounds 2 and 9 are isostructural 2D layer with a 3-connected hcb topological net. Similar to 2, compound 3 also displays a 3-connected 2D hcb topological net. Compounds 5 and 10 are a 2D layer with a 4-connected sql topological net. Compound 6 shows a chiral 2D layer based on a 1D left- or right-handed helical chains, which are further extended into an achiral 2D + 2D -> 3D supramolecular network by hydrogen bonds with alternately arrangement. Compound 7 features an unusual 2-fold interpenetrating 3D coordination network which exhibits a new intriguing (3,5)-connected binodal topological net with the Schlafli symbol of (5(2). 6)(5(3).6(3).7(3).8). Compound 8 shows a 2D -> 43D supramolecular structure based on (3,4)-connected 2D bilayers with the Schlafli symbol of (4(4).6(2)). Compound 11 displays an unusual three-dimensional coordination network which exhibits an intriguing (3,8)-connected binodal new topological net with Schlafli symbol (4(2).6(2))2(4(2).6(23). 83). Compound 12 features a two-fold interpenetrating (3,4)-connected 3D framework with the fse topological net. Compounds 1-12 were obtained under similar reaction conditions. The diverse structures indicate that rational selection of the second ligand, metal salt, counter anion and solvent are good methods to further design metal-organic compounds with new structures and properties. Moreover,, their thermal stabilities, photo luminescent and magnetic properties were also investigated. More importantly, compound 12 has been successfully applied in the detection of Fe3+ ion in DMF solutions and nitrobenzene and the possible detecting mechanism was also discussed.