| In recent years, the most important subjects of intensive current research in coordination chemistry, supramolecular chemistry and crystal engineering have been focused on the rational design, syntheses, crystal structures and properties of complexes, especially the coordination polymers. Many muti-function ligands, such as carboxylic acids and pyridines related ligands, owing to their potentially employing functional groups of participating in both coordination bonds and weaker non-covalent interaction, have been used in the construction of complexes. In this research, a series of new complexes of unsaturated carboxylate copper(Ⅱ) have been prepared by several kinds of methods have been used, for example conventional solution, diffusing method and hydrothermal reaction methods, and their crystal structures and properties were determined. In this paper, the main results are as follows:First, eight novel copper(II) complexes with unsaturated dicarboxylates [Cu(malXtpy).(H2O)4]n (1), [Cu(mal)(dpa)]n (2), [Cu(OH)(fum)0.5(dpa).H2O]n (3), [Cu(mal)(bipy).(H2O)2]n(4), {Cu2(rum)2(tpy)2.(H2O)4}∞(5), [Cu(fumXtpy).(H2O)5]n (6), {[Cu2(fum)(bipy)4][ClO4]2}∞ (7)和{[Cu2(mal)2(phen)2](CH3OH)2(H2O)4}∞ (8) have been prepared and characterized by elemental analysis, IR spectra, thermal analyses, magnetic investigation and UV - Visible spectroscopy.In complexes 1-8, the coordination modes of acid ligand and the supramolecular structure are different. Complex 1 is constructed into 2D zipperlike layers by the unprecedented aromatic π-π stacking interactions and hydrogen bonds. These layers are constructed through hydrogen bonds to result in a 3D supramolecular network with 1D open channels which void size is 12.924×8.329 A, in which exists an unprecedented one-dimensional water chain. In complex 2, the maleate anions provide the first example of maleate to serve as a monodentate/chelating tridentate bridging ligand, and each pair of 1D chains recognize each other through strong hydrogen bond and aromatic π-π stacking interactions to generate a zipperlike double-stranded chain. In complex 3, the hydroxyl anions and the fumarate ligand provide as bridging ligand to bridge copper centers constructing 1D chains. 1D chainsrecognize each other through strong hydrogen bond and aromatic jt-jt stacking interactions to generate 3D supramolecular structures. In complex 4, carboxylate anions exhibit in monodentate and syn, anti-nl:iil:u2 conformations, bridging two copper centers giving rise to a 1-D zigzag chain.A solution of tpy reacts with rumarate Cu(II) salt to yield two novel fumarate bridged coordination complexes 5 and 6 of general formula, which is binuclear complex for 5 and ID chain for 6. In complex 6, the ID chains interlace with an unprecedented one-dimensional water chain to form 3D supramolecular structures.Complexes 7 and 8, are both binuclear complexes. Complex 7 forms the twofold interpenetrated 3D supramolecular structures by hydrogen bond and n-it interactions. Complex 8 forms the 3D supramolecular structures with channel system by hydrogen bond and %-n stacking interactions.Second, six novel copper(II) complexes with unsaturated carboxylates {Cu2[O2CC(CH3)=CH2]4(4,4'-bipy)}n(9), {Cu2(CH2=C(Me)CO2)4-2H2O}a)(10), {Cu2(CH2=C(Me)C02)4-2(apy)}oo(ll), {Cu(CH2=C(Me)CO2)2(Hdpa)-H2O}? (12), {Cu(CH2=CHCO2)2(Hdpa)-H2O}00 (13) and {Cu(CH3-CH=CH-CCO)2(Hdpa)^20)}oo(14X have been prepared and characterized by elemental analysis, thermal analysis, I.R., c.v. and UV - Visible spectroscopy.The X-ray structure analyses of 9 show a one-dimensional chain structure where the binuclear paddle-wheel structural units are bridged by 4,4'-bipyridine molecules. Furthermore, the binuclear units between adjacent layers can form channel system, and the size of the void is 0.9430 * 1.3831 nm. Complexes 10 and 11 are the binuclear paddle-wheel structural complexes. The temperature-dependent magnetic susceptibility of 9, 10 and 11 indicates that the strong antiferromagnetic interaction exists between copper(II) atoms in the binuclear units. In complex 12 and 13, the water molecular participated in the formation of the ID double-chain for 12 and 2D layer-columnr supramolecular structure for 13 by hydrogen bonds but non-coordinated with copper(II) atom. In complex 14, the water molecular coordinating with copper(II) atom participated in the formtion of the ID stair double-chain columnr supramolecular structure by hydrogen bonds and %-n stackingalong the crystallographic a-axic.Thirdly, complex {Cu(SO4)(tdpa)(H2O)-H2O}0O(15) is mononuclear complex and the copper atoms have distorted trigonal-bipyramidal environment. Each mononuclear molecules are constructed with the neighbor same directional molecules through hydrogen bonds resulting in a ID supramolecular chain. The ID supramolecular chains arranging as AB AB type form 2D supramolecular structure.
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