| Supramolecular chemistry, defined as the subject of study on the formation of new chemical structures by the self-assembly of molecular sub-units together through weak intermolecualr interactions, is at the foreland of the molecular sciences. The supramolecular building block as one of the important parts of supramolecular chemistry has been used for the rational design and syntheses of supramolecular compounds with novel structures and application. The intermolecular interactions and recognition mechanism made these building blocks constructed together to form supramolecular networks with ideal structures, functions and steady properties. Coordination and hydrogen bonds are the most widely used tools in this assembly process. In this paper, we reported ten novel supramolecular compounds by hydrothermal synthesis and traditional synthesis techniques. Their crystal structures have been determined by X-ray diffraction methods. We found the choice of metal ions, organic ligands and sythesis conditions have great influences on their supramolecular assembly. In addition, we measured their optical properties, including third-order non-linear optical properties and fluorescence, and found these compounds possess good optical properties. Our work is listed as follows: (1) Three inorganic-organic hybrid supramolecular compounds constructed by mixed ligands, including NCS-and different sized heterocyclic ligands, have been synthesized and we measured their single-crystal structures. [Cu(im)2(NCS)2] 1: P21/n, a =7.672(8)?, b=5.722(4)?, c=14.083(10)?, β=100.07(5)o, V=608.6(9) ?3, Z=4, Dc=1.724 g/cm3, shows one-dimensional chains generated by bridged thiocyanate groups. Then N-H···S hydrogen bonds and π-πinteractions constructed three-dimensional supramolecular framework. [pipH]2[Co(NCS)4] 2: P21/n, a=6.7778(14)?, b=11.876(2)?, c=12.110(2)?, β=101.57(3)o, V=954.9(3) ?3, Z=4, Dc=1.619g/cm3, exhibits a novel two-dimensional layer constructed by N-H···N and S···S interactions. [dabcoH]2 [Ni(NCS)4] 3: P21/n, a=7.180(2) ?, b=11.198(3) ?, c=14.348(6) ?, β=96.89(3)o, V=1145.3(7)?3, Z=4, Dc=1.500 g/cm3, consists of two-dimensional supramolecular layer with hourglass-shaped cavities constructed only by N-H···S. We found thiocyanate anion is a very versatile ligand and plays an important role in constructing the supramolecular networks. In addition, the size of ligands have a great influence on the assembly structures. (2) Two Cu(II) coordination polymers constructed by mixed aliphatic carboxylic acids and nitrogen-containing ligands have been obtained. [Cu2(OOCCH3)4(4,4'-bpy)]·DMF 4, P1, a = 7.389(3)?, b=8.355(4)?, c=11.361(8) ?, α=78.54(5)?, β=85.95(4)?, γ= 64.01(3)?, V=617.8(6)?3, Z=1, Dc=1.593 g/cm3, shows a novel one-dimensional chain generated by bridged 4,4'-bpy ligand. [Cu(OOCCH2COO)(DMF)] 5, P43, a = 8.4221(12) ?, b = 8.4221(12) ?, c = 12.049(2) ?, V = 854.6(2) ?3, Z=4, Dc = 1.855 g/cm3,exhibits three-dimensionaldiamond topological structure formed only by malonate. We found the organic ligands have an important effect on the formation of assembly structures. (3) We synthesized and characterized two Prussian-blue supramolecular compounds, and resolved their single structures. [Ni(dien)2][Fe(CN)4] 6 P21/c, a=15.137(3)?, b=9.4560(19)?, c=15.260(3)?, β=112.01(3)o, V=2025.1(7)?3, Z=4, Dc=1.374g/cm3; [Ni(dien)2]2[Fe(CN)6]·4H2O 7 P21/n, a=9.243(4)?, b= 14.538(4)?, c=13.858(5)?, β=90.94(2)o, V= 1861.9(11)?3, Z=4, Dc=1.431 g/cm3. The chalating capacity of ligands greatly affected on the coordination ploymers'networks. Although in the whole reaction the dosage of dien is very small, its strong chalating capacity makes the all coordination space of Ni(II) occupied and CN-not participate in the coordination with Ni(II). So the obtained compounds are the supramolecular network on the base of simple ionic compounds. (4) A novel one-dimensional chain coordination polymer has been obtained by SO42-as bridging ligands and phen as chalating ligand. The structural data of [Cd(phen)(H2O)2SO4]n 8 are listed as follows: P212121, a=6.8286(3)?, b= 10.3533(5) ?, c= 20.0827(9) ?, V=1419.82(11) ?3, Z=4, Dc=1.987 g/cm3. Because the phen ligand exhibits the strong ability to chelated metals to form interdigitation structures and also can construct supramolecular network via C-H···O hydrogen bonds and π···πstacking aromatic interactions, a three-dimensional interdigitation supramolecular network has formed. Experiment shows that this compound exhibits strong fluorescent property. (5) We synthesized two organic acid-base cocrystals constructed by 1, 2, 4, 5-benzenetetracarboxylic acid and aza donor molecules. Cocrystal [(HIN)+(H3BTA)-H2O] 9, P-1, a = 9.640(6) ?, b=10.009(5)?, c=10.744(5) ?, α= 99.07(3)o, β= 114.06(4)o, γ= 110.54(3)o, V=829.7(8) ?3, Z=2, Dc=1.582g / cm3...
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