| Rational design and synthese coordination supramolecules with novel topology through molecular recognization and assembly, especially for coordination polymers and supramolecular complexes, represents a topical and current research interest in the directions of chemistry, materials, medicals and biology and the intense interest in this field has resulted not only in supplying useful information about the constructing, entangling even topological linking by covelent and incovelent interactions of molecular entities, but in both unusual physical, chemical behavior and potential applications as optical, electronic, magnetic, catalytic materials, molecular recognition, absorbent, ion exchange, gas storage and biology activity. Lately, it is demonstrated that rationnal design and considerate selecting special organic structure baset through appropriative approach of assembly should to be the key in constructing target polymers and which is a stubborn challenging work for scientists either. In this research, 16 new complexes of transition metals based on 2-(2'-pyridyl)benzimidazole (Hpb) with biological activity and two pyridylamine ligand, 2,6-bis(2-pyridylamino)pyridine (tpda) and bis[6-(2-pyridylamino)pyrid-2-yl]amine (teptra) reaction with organic carboxylate in variety conditions have been prepared. They are Hpb (1), [Cu4(pb)4(cro)4(MeOH)2]·2MeOH (2),[Cu2(pb)(Hpb)(mac)3(MeOH)] (3), [Cu(Hpb)(acr)2(H2O)] (4),{[Cu(Hpb)(mal)]·H2O}n (5), [Cu(Hpb)2(NO3)]NO3 (6), [Co(bpdc)(Hpb)(H2O)]n (7), tpda (8), [Cu(tpda)(fum)(H2O)] (9), [Ni(tpda)2]-(mal)-(H2O) (10), [Ni(tpda)2]·(NO3)2 (11), {[Co(bpdc)(tpda)]·1.5H2O}n (12), {[Co(HCOO)3]·2.5H2O}n (13), [Cu(teptra)(dhbd)]·CH3OH (14), [Cu(teptra)(mac)]·mac (15),[Co(phen)3]·(Hhbd)·H2O (16) which have been determined by the X-ray single crystal diffraction analysis, elemental analysis, IR spectra, UV-Visible spectroscopy, Fluorescence spectroscopy, thermal analyses, cyclic voltammograms and temperature dependence of magnetic susceptibility measurement to investigate the spectroscopy characters and properties. The result shows, that ligand Hpb(1) presents two states in complexes: neutral and deprotonation. As it combine with unsaturated organiccarboxylate copper with dinucleus cage architecture, the structures of the resulted complexes 2, 3, 4, 5 changed different from the metal source. Ligand tpda(8) and teptra both have meso-helical configuration with big steric hindrance, and the multi-dimensional supramolecular complexes 9,10,11,14,15 based on them are built by coordiantion bonding, hydrongen bonding and stacking interactions. Interestingly, complex 7 and 12, the two one-dimensional polymeric chains synthesized by hydrothermal reaction with 4,4'-biphenyldicarboxylic acid (Fkbpdc) bridged metals with different type, form distinct topologies as the result of introducing dissimilar terminal ligand Hpb and tpda, the former gives rise to a supromolecule containing an overall entanglement hydrogen bonding networks, poly(pseudo-rotaxane), while the latter makes a three-dimensional supramolecule with open tunnels. The most attention should be paid to complex 13, which is obtained by replacing bpdc in complex 12 with 1,4-phenyldicarboxylic acid, a beat all architecture: a novel topological net connected by formate with NaCl crystal lattic characteristic. In addition, 1,4-phenyldicarboxylic acid also does not coordinate to metal ions in complex 6, in fact, two Hpb bond to copper center. It is found that in the hydrophiled tunnels of complex 16, free water molecules display one-dimentional wavelike chains, perpendicular with dissociative 2-hydroxybutanedioic acid chains. Meanwhile, it comes to some disciplinary conclusion on analysis of structures, assembly rules, spectroscopy characters and electrochemistry properties of supramolecular polymers constructed from these two kinds of multi-nitrogen heterocyclic ligands.
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