| Recently, inorganic-organic hybrid material, microporous material, monomolecular magnet and coordination polymers are the new research fields in the crystal engineering. The potentially applications of these compounds will be intensive in the fields of chemistry, material, medicines and biology.The construction of supramolecular polymeric networks is of great interest in recent years, not only for their intriguing architectures and topologies, but also for their potential properties as functional solid materials in NLO properties, molecular recognition, ion exchange, catalysis, magnetism etc.In this paper, novel cluster and coordination polymers were designed by treatment of metal halides/pseudohalides with organic ligands. We found it is rarely studied at present. Therefore, it belongs to the leading field of crystal engineering. Eight novel clusters and coordination complexes were obtained by treating six nitrogen-containing ligands with metal halides/pseudohalides via the method of solvent diffuse and solvent volatilization at room temperature. Furthmore, we have investigated their syntheses, structural analyses, and fluorescence properties.Firstly, through the assembly of CuSCN,HgI2 and ligands L1～L5, coordination polymers 1～5 are generated: {[Cu(SCN)2(DMSO)2(dpb)] (DMSO)}n (1), [Cu(SCN)2 (bpp)2]n(2),[HgI2(4-bpce)3] (3), [HgI2(3-bpfob)]n (4), [CuSCN(4-bpfob)(H2O)]n(5). 1～4 give one-dimensional chain complex, 2～5 are two-dimensional net coordination polymers. 2 is an arrangement of corrugated 2-D nets based on the (4, 4) topology, but 5 shows a 2-D network with binuclear metallamacrocycle by two bridging SCN-. In the two coordination polymers 2 and 5, the ligands have two conformations. 3 is binuclear metallamacrocycle, two neighboring Hg(II) ions and two bridging ligands form an inner cavity with the size of 13.025×12.663A2.Secondly, the reactions of CuI with L5～L6 ligands afford three new cluster coordination polymers [CuI(3-bpfob)]n(6), [CuI(4-bpfob)(DMF)(CH3CN)]n (7), [CuI(bpit) (THF)(H2O)]n (8). 6,7 and 8 contain Cu(μ2-I)2Cu rhombohedron which is formed by two bridging iodides binding to two symmetry related Cu(I). The Cu(μ2-I)2Cu units connecting two couples of bidentate 3-bpfob, 4-bpfob, bpit ligands form 1-D infinite chains. 6 is helical double-stranded 1-D coordination polymer, 7 and 8 are double-stranded 1-D coordination polymers.
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