| Recently, metal-organic supramolecular complexes have been studied extensively because of their wide range of applications in optical, electricity and magnetic fields. This thesis focuses on synthetic routes, structural studies and characterization of complexes constructed by trinickel metal string building block and complexes constructed by sulfonic and neutral different nitrogen-containing ligands with various metal ions.17 trinickel complexes have been synthesized. In these complexes, trinickel unit [Ni3(dpa)4]2+ is the building block and axial ligands are aromatic dicarboxylic acids, aromatic monocarboxylic acids, aliphatic dicarboxylic acids and ligands containing N, S, or P. In the synthesis of sulfobenzoate metal complexes, we chose Zn, Sn and Ni as the metal ions, 2/3/4-sulfobenzoate (2/3/4-sb) as the acid ligand, and 2,2'-bipyridine (2,2'-bipy), 4,4'-bipyridine (4,4'-bipy),1,10-phenanthro line (1,10-phen), or 1,2-di(4-pyridl)ethylene(bpe) as the neutral ligands and 18 complexes have been synthesized and characterized. Additionally, the structures of 2 sulfobenzoate complexes with mono-protonated sulfobenzoate and neutral ligands have been studied. In all, we totally analyzed 37 complexes with their crystal structures and characterized them with IR, element analysis, TG, UV/vis, and photo luminescent. CV and magnetic analyses are only for trinickel complexes.In trinickel complexes, [Ni3(dpa)4]2+ framework is the building block and the structures and properties of trinickel complexes were investigated by changing the different axial ligands. The structures of trinickel complexes are probably different when the different axial ligands are introduced and 1D or 0D is their common molecular assembly. In the synthesis of trinickel complexes, three-layered solution method was used. When the aromatic dicarboxylic acids were used as the axial ligands, one 0D and four 1D complexes were synthesized, [Ni3(dpa)4(1,2-Hbdc)2]·CH2Cl2·H2O(1),{[Ni3(dpa)4(1,2-bdc)]·1.5H2O}n(2), {[Ni3(dpa)4(1,2-nbdc)]·1.5H2O}n(3),{[Ni3(dpa)4(bdc)]·0.5H2O}n(4), and [Ni3(dpa)4(1,4-nbdc)]n(5). When the aliphatic dicarboxylic acids were chosed to be the axial ligands, four trinickel complexes were obtained. {[Ni3(dpa)4(OOCCOO)]·CH3OH·0.5H2O}n(6), {[Ni3(dpa)4(COOCH2COOH)2]·[ClO4]-·[Ni3(dpa)4(COOCH2COOH)(H2O)]+·2H2O}( 7),{[Ni3(dpa)4(fum)]·(fum)0.5·3H2O}n(8), and [Ni3(dpa)4(syn-OOCHC=CHCOOCH3)2][Ni3(dpa)4(syn-OOCHC=CHCOOCH3)(H2 O)](ClO4)(9), in which complexes 6 and 8 are 1D chains while complexes 7 and 9 are 0D structures. When the aromatic monocarboxylic acids act as the axial ligands, three complexes were synthesized, Ni3(dpa)4(3-nbc)2(10), Ni3(dpa)4(4-nbc)2(11), and Ni3(dpa)4(3,5-nbc)2(12). Besides, five complexes containing N, S, or P were synthesized, [Ni3(dpa)4(2,3-pzdc)]n(13), Ni3(dpa)4(2-thiophenecarboxylate)2(14), [Ni3(dpa)4(H2O)2]2+[OOCC6H4SSC6H4COO)]2-·2H2O·2DMF (15), Ni3(dpa)4(H2PO4)2·4H2O(16), and [Ni3(dpa)4(HPO4)]n(17), in which 13 and 16 are 1D polymers. Currently, few 1D complexes containing trinickel core were reproted. We reported eight 1D metal string complexes.In the Zn2+/4-sb/phen system, we explored the influences of the ratio of reactants, starting materials, synthetic methods, reaction time, and reaction temperature on the structural assemblies, leading to four diverse complexes, namely [Zn(phen)2(2H2O)](4-Hsb)(NO3)·2H2O(18), [Zn(phen)2(2H2O)](4-sb)·4(H2O)(19), [Zn(4-sb)(phen)(2H2O)]·H2O(20),and [Zn(4-sb)(phen)(H2O)]n(21). The raltionship between synthetic environments and structures was discussed. Further, we investigated the influence of 2,2'-bipyridine and/or 4,4'-bipyridine on the supramolecular assemblies of the Zn2+/4-sb system, generating three new complexes, [Zn(4-sb)(2,2'-bipy)(H2O)3]·H2O(22),{[Zn(4,4'-bipy)(H2O)4]·(4-sb)}n(23), and [Zn(4-sb)(2,2'-bipy)(4,4'-bipy)0.5(H2O)]n·2H2O(24). In 22, the 4-sb bidentately chelates to the Zn2+ ion. In 23, the 4-sb is a counter ion, while in 24, the 4-sb acts as a bridging linker. In the Zn2+/2-sb system, many efforts led to two polymers, {[Zn(2-sb)(phen)(2H2O)]·2H2O}n(25) and{[Zn(2-sb)(4,4'-bipy)(H2O)]·H2O}n(26). The molecular structure of 25 is a 1D chain extended by 2-sb through the bridging action of the sulfonate. The structure of 26 is a 2D layer constructed by both 2-sb and 4,4'-bipy. We further explored the influence of two neutral ligands on the Zn2+/4-sb assemblies, giving two complexes, [Zn(4-sb)(phen)2(H2O)]·0.5(4,4'-bipy)·3H2O(27) and {[Zn(4-sb)(phen)(bpe)1/2]·2H2O}n(28). In 27, the 4-sb adopts a monodentate coordination mode and the 4,4'-bipy only exists as a guest molecule. In 28, each 4-sb coordinates to two Zn2+ ion through its carboxylate and sulfonate and both the bridging 4-sb and bpe extend the structure into 1D chain. Moreover, we carefully analyzed the hydrogen bonds andπ···πstacking interactions in these eleven Zn2+ complexes.In the Sn2+/sb system, five monomers were synthesized, [Sn(CH3)3 (4,4'-bipy)(4-sb)](4,4'-H2bipy)0.5·(H2O)(29), [Sn(CH3)2(phen)(4-sb)(H2O)]·2H2O(30), [Sn(CH3)2(4-sb)(2,2'-bipy)]·2H2O(31), [Sn(CH3)2(3-sb)(phen)]·5H2O(32), and [Sn(CH3)2(3-sb)(2,2'-bipy)(H2O)](33). Hydrogen bonds andπ···πstacking interactions were carefully analyzed. Theπ···πstacking interactions in these complexes are strongly related to the anti-cancer activities.In the Ni2+/4-sb system, two diverse complexes [Ni(4-sb)(phen)(H2O)]·(2H2O)(34) and [Ni(phen)3]·(4-Hsb)·(OH)·(8H2O)(35) were synthesized and characterized. Complex 34 is a monomer, while complex 35 is a cation-anion species. Both extending structures are 3D hydrogen-bonding networks. It is worth noting that in the complex 35, co-existence of base and acid is observed.Finally, two structures of 1:1 proton transfer complexes of sulfobenzoic acids and aromatic amines were synthesized, C12H11N2·C7H5O5S(36) and C12H9N2·C7H5O5S·2H2O(37). Mono-protonated sb ligands and protonated neutral ligands generate 3D supramolecular structures through hydrogen bonding, respectively.
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