| In this presentation, we report the syntheses, crystal structures and properties of the metal coordination complexes constructed from 5-sulfosalicylate (H3ssal). In the procedures of syntheses, we chose 2,2'-bipyridine (2,2'-bipy), 4,4'-bipyridine (4,4'-bipy), 1,10-phenanthroline (1,10-phen), 2-aminopyridine (2-ampy), benzimidazole (BD) and trans-1,2-bis(4-pyridyl)ethylene (bpe) as neutral ligands, and Pb, Cu, Co, Zn, Cd and Mn as metal ions in our research. Totally thirty compounds were synthesized, and have been characterized by X-ray single crystal diffraction, IR spectrum, element analysis, TG and photoluminescent.For copper complexes, we focused on the effect of the reaction conditions (reactants, the molar ratio, temperature and solvent), and neutral ligands on the structures. We discussed eight copper complexes: [Cu(Hssal)(2,2'-bipy)(H2O)2]n(1), [Cu4(CH3COO)2(ssal)2(2,2'-bipy)4(H2O)2]·6H2O (2),{[Cu(ssal)(2,2'-bipy)][Cu2(ssal)(2,2'-bipy)2(H2O)2](H2O)}n (3),{[Cu3(ssal)2(dpa)3]·3H2O}n (4), [Cu2â…¡(ssal)2(dpa)2][Cuâ… (dpa)2]2·2H2O (5), {[Cu(ssal)(H2O)](2-ampy)}n (6), {[Cu3(ssal)2(BD)6]·8H2O}n (7),[Cu(TTF)(phen)(H2O)][Cu(TTF)(Hssal)(phen)] (8). The framework is one-dimensional chain in 1, tetraneutral in 2, two one-dimensional cationic-anionic chains in 3; all of which are extended to three-dimensional network by hydrogen bonding. 4 has two-dimensional layer network, however, in the similar synthesis condition, 5 is a mixed-valence copper complex. Both 6 and 7 are one-dimensional structures. 8 is a cationic-anionic complex. In complexes 1 and 8, H3ssal ligands are doubly deprotonated and remain phenol protons; while in the other six compounds, they are fully deprotonated. There are seven coordination modes of 5-sulfosalicylates in the eight complexes.For lead complexes, we focused on the effect of neutral ligands (chelating and bridging) on the structures. There are eight complexes synthesized and characterized: [Pb(Hssal)(2,2'-bipy)(DMF)]n (9), [Pb(Hssal)(2,2'-bipy)(H2O)]n (10), [Pb(Hssal)(phenXDMF)]n (11), [Pb3(ssal)2(phen)3]n (12),{[Pb(Hssal)(2,2'-bipy)](4,4'-bipy)0.5}n (13), Pb2(2,2'-bipy)2(4,4'-bipy)(Hssal)2(H2O)2] (14), [Pb(phen)(4,4'-bipy)0.5(Hssal)]n (15), [Pb(Hssal)(2,2'-bipy)(bpe)0.5]n (16). Complexes 9 and 11 are isostructural, consisting of one-dimensional ladder-like chains. 10 is a two-dimensional double-layer architecture, while 12 is a two-dimensional layer network. The structure of complex 13 possesses a one-dimensional ladder-like chain with guest 4,4'-bipy molecules, while the molecular structure of complex 14 is a dimeric species with a coordinating 4,4'-bipy ligand. Complex 15 consists of a one-dimensional ladder-like chain with monodentate 4,4'-bipyridine but somewhat different from that of complex 13. Complex 16 is a two-dimensional layer structure. The coordination spheres of Pbâ…¡ions in 9-16 are controlled by three factors: the activity of a lone pair of electrons, weak Pb-0 interactions, andÏ€-Ï€stacking interactions. The Pbâ…¡lone pairs in 9,11 and 16 are inactive, whereas in the other five complexes, they are stereochemically active. Except in 12, H3ssal is fully deprotonated, while in the other seven complexes, it only loses two protons. 5-Sulfosalicylate anions have six coordination modes in the eight complexes.For transition metal Co and Zn, we have synthesized two cationic-anionic complexes: [Co(phen)2(H2O)2](Hssal)·4H2O (17) and [Zn(phen)2(H2O)2](Hssal)·4H2O (19), which act as the reactants for the secondary synthsis, and two mixed-metal complexes have been gotten: {[Co(phen)(H2O)4][Cu2(phen)2(ssal)2]·5H2O (18) and [Zn2(μ-OH)2(phen)2(H2O)2][Cu2(phen)2(ssal)2]·3H2O (20). 17 and 19 are isostructure, where Hssal2- ions are free ligands and act as counter ions. In 18 and 20, Hssal2- ligands are further deprotonated and coordinated to metal ions.Hydrothermal in situ ligand synthesis has been rapidly developed over the past several years due to its effectiveness, simplicity and environmental friendliness. However, up to now, most of the mechanisms of the in situ ligand syntheses have not been very clear. We have discovered three hydrothermal in-situ reactions in the process of synthesizing 5-sulfosalicylate complexes: the redox of Cu(â…¡), decarboxylation and hydrolysis. Eight products of in-situ reactions have been obtained and characterized: {[Cuâ… Cuâ…¡(ssal)(2,2'-bipy)(4,4'-bippy)]·2H2O}n (21),{[Cuâ…¡(ssal)2][Cu4â… (4,4'-bipy)4(H2O)]·5H2O}n (22), [Cu(2,2'-bipy)2Cl]·(4-HBS)·2H2O (23),[Cu(2,2'-bipy)2Cl]·(4-HBS)·(1 ,4-dp)0.5·H2O (24),{[Cd3(CH3COO)4(4,4'-bipy)4](HBS)2·10H2O}n (25),[Cd(4,4'-bipy)2(H2O)4](HBS)2·4H2O (26), [Mn(4,4'-bipy)2(H2O)4](HBS)2·4H2O (27), {[Co(4,4'-bipy)(H2O)4](HBS)2·3H2O}n (28). Both 21 and 22 are mixed-valenced copper complexes, and 21 is a two-dimensional network, while 22 consists of one-dimensional chain. 23 only contains the decarboxylation product, 4-hydroxybenzenesulfonate ion is free ligand and acts as counter ion. However,24 contains both decarboxylation and hydrolysis products, both of which are free ligands, acting as counter ions or guest molecules. Complexes 25-28 only exist the products of decarboxylation, which are also free ligands. 25 is two-dimensional layer network, while 28 consists of one-dimensional chain. 26 and 27 are isostructural, mononeutral.DMF can take hydrolysis reaction under reflux or hydrothermal conditions, and the product, formate, can coordinate to metal ions. Two complexes containing the hydrolysis products of DMF have been synthesized and characterized: {[M(COO)(H2O)2(4,4'-bipy)]2[M(4,4'-bipy)(Hssal)2(H2O)2]}n (M=Cd, 29; Mn, 30). These two complexes are isostructural and consist of one-dimensional chains, further extended into three-dimensional network by hydrogen bonding. |
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