Synthesis, Crystal Structures And Properties Of Metal Ions Complexes Base On Sulfonate Ligands

In recent years, as the Metal-Organic Coordination polymers have special properties and diversiform structure, have extensive potential application in many fields such as NLO, magnetics, catalyst, molecule carriers, gas storage and ergonomics. The design and synthesis of coordination polymers with porous structures continues to be a wide-spread growing field, its exploration is driven in part by the search for novel optical and electrosensitive materials as well as for novel porous sorbents and catalysts. The selective uptake of specific transition-metal ions from aqueous solutions has also aroused considerablie attention. Porous coordination frameworks, containing phosphates groups, sulfonate groups, could be served as potential candidates in heavy metal ion sorption by the result of their multiple coordination knots and many coordination modes. Meanwhile, ferrocene-based porous materials could also be widely used in the research of optical and electrochemical materials. So the study of the Metal-Organic frameworks enriched the study of the theories base on sulfonate groups. In order to systematically investigate the coordination chemistry of sulfonate ligands and then find some laws as well as expect to acquire some novel model complexes, we choose the pyridine-2-sulfonate(2-pSO3H) , N-(2-hydroxybenzy) aminoethanesulfonic acid (H2Saes) ,N-(2-hydroxybenzy)aminomethanesulfonic acid (H2Sams) as ligands interacting with metal ions asour research subject. In this paper, based on the previous studies together with more than oneyear's investigation, twenty-fives novel complexes were synthesized. They are analyzed and characterized by IR spectrum, elemental analysis, TGA, XRPD, X-ray single crystal diffraction techniques, gas adsorption, magnetic and Luminescent properties of some compounds have also been investingated. They are: (1){[Cu(2-pSO3)3 ][Cu(4,4'-bpy)2(H2O)]·(H2O)(NO3)}n; (2)[Cu(2-pSO3)2 (4,4'-bpy)2] n·nH2O ; (3){[Cu(2-pSO3)2(1,3-bpp)2]·(H2O)3}n; (4){[Cu(2-pSO3)2(1,2-bpe)]·2H2O}n; (5){[Cu2(2-pSO3)2 (4,4'-bpy)4]·(ClO4)2 }n; (6)[Cu(2-pSO3)(4,4'-bpy)2] n·nH2O; (7)[Mn(H2O)4(4,4'-bpy)2]·(2-pSO3)2; (8){[Mn2(2-pSO3)2(Ac)2 (4,4'-bpy)2]·(4,4'-bpy)}n; (9){[Mn2(2-pSO3)2(Et-COO)2 (4,4'-bpy)2]·(4,4'-bpy)}n; (10){[Mn2(2-pSO3)2(Ph-COO)2(4,4'-bpy)2]·( CH3OH)}n; (11)[Ni (2-pSO3)2 (4,4'-bpy)2]n·(H2O) ; (12)[Zn(2-pSO3)2(H2O)2] ; (13){[Zn2(2-pSO3)2(Ac)2 (4,4'-bpy)2]·(4,4'-bpy)}n; (14)[[Ag(2-pSO3)(4,4'-bpy)2]; (15)[Zn(Saes)(4,4′-bpy)2(H2O)]n·nH2O; (16)[Cd(Saes)2(4,4′-bpy)2(H2O)2]n·nH2O (17)[Co2(Saes)2(4,4′-bpy)4(H2O)2]n; (18)[Cu(Saes)2 (4,4'-bpy)2 (H2O)2]n·nH2O; (19){K[Ni(Ac)(Sams)]6}·[Na(H2O)6]; (20)[Cd1.5(Ac)2(4,4′-bpy)1.5]n·[(CH3OH)(HSams)(H2O)3]n; (21)[Zn(Sams)(2,2′-bpy) (H2O)]2·[(CH3OH)(H2O)4]; (22)[Zn(Sams)(phen)(H2O)]2·3H2O; (23)Cu2(Sams)2(4,4'-bpy) (H2O)2]·H2O; (24)[Cu2(Sams)2(1,3'-bpp) 2]; (25)[Cu(Sams)(2-ampd)(CH3OH)]21,Two novel 2-D network structure: (1)⁶; have been synthesized by the reaction between pyridine-2-sulfonate(2-pSO3H) and different copper salts. Single crystal X-ray diffraction shows that complex (1) crystallized in monoclinic, space group P2(1)/c. And a C-H···πinteraction with H(3)···centroid distances of 3.53 ? which interlink the adjacent chains also exist between pyridine rings,Ï€-Ï€interaction of pyridine rings and intermolecular hydrogen bonds make great contributions to form 1 D supramolecular. And 1 D supramolecular as a guest molecular througth a 2-D metal-organic framework(host molecular). (4) was synthesized by reaction of Cu(ClO4-)2·6H2O, 2-pSO3H and 4,4'-bipyridine in aqueous methanol (1:1,v:v) under the condition of adjusting the pH=6. Two adjacent copper atoms(6.799 ?) are linked by O-S-O (sulfonate group) chains forming eight-membered rings involving two different copper atoms and building up one-dimensional chains,and 4,4′-bipy bridging the chains which form 2D network structure. (2)as a 1D rigid, linear coordination polymer, (4,4'-bipyridine) (2-pyridylsulfonate) copper, has been applied for the design and synthesis of a new porous host that generates 1D interlinked lattice voids by an interdigitated packing motif through the recognition of hydrogen bonding andÏ€-Ï€stacking. The porous structure is architecturally robust when it reversibly uptake water molecules and exchange guest small molecules (MeOH, 1·i-PrOH) from solution as determined by single-crystal-to-single-crystal transformation studies. Moreover, the open-channel solid displays interesting benzene and toluene gas sorption behaviors with large hysteresis and incomplete desorption, being attributed to a widening of the channel cross-section that restricts the passage of the larger guest molecules, resulting from dynamic lattice voids of the"soft"supramolecular framework. (3) and (4) were 1D interesting zigzag infinite chain structure.For complex 3, the layers are stacked one above the other in the third dimension, it results in the formation of a special 1D supramolecular MOF (Metal Organic Framework) with 1D channel. However , the layers of complex 4 are stacked one above the other in the third dimension, it results in the formation of a special 3D supramolecular MOF with 1D channel and guest molecular were located in1D channel.Complex 5 bothÏ€-Ï€interaction of benzene and pyridine rings and a number of intermolecular hydrogen bonds between 1D chain to construct three dimension supramolecular Metal Organic Framework with 1D channel and guest water molecular were located in the channel.2,Eight complexes of 2-pSO3H have synthesized with different transition metal or adding the second ligands. As follow (6)¹⁴; Complex 7 has been synthesized by the reaction between pyridine-2-sulfonate (2-pSO3H) and solution of 50% Mn(NO3)2 under the condition of adjusting the pH=6. Single crystal X-ray diffraction analysis indicates that complex 7 crystallizes in Monoclinic, space group P2(1)/c. The ligand pyridine-2-sulfonate didn't coordinate to centre MnII and acted as anions exist outer. Complex (8) (13) were obtained by reaction of 2-pSO3H and ZnAc2·2H2O,MnAc2·2H2O in methanol-water mixed solution,which belong to Triclinic, space group P-1. The Mn (II) center has the same coordination environment and structure to complex (12) (17) and they are allomers to one another. TheÏ€-Ï€stacks of pyridine rings from adjacent chains extended it into 2D grid structure and uncoordinated 4,4'-bipy act as guest molecule existing into 2D grid structure attribute to hydrogen bonds between uncoordinated 4,4'-bipy and free oxygen atom of the sulfonate group with another hydrogen atom of the carbon hydrogen from 4,4'-bipy ligand.. Complex(13) was obtained by reaction of 2-pSO3H and MnCO3,CH3CH2COOH in methanol-water mixed solution,which belongs to Triclinic, space group P-1. The structure of 9 was similar to complex (8). Complex (10) has been synthesized by the reaction between pyridine-2-sulfonate (2-pSO3H) and MnCO3,ph-COOH , which belongs to Triclinic, space group P-1. TheÏ€-Ï€stacks of pyridine rings from adjacent chains formed into 2D network structure and MeOH act as guest molecule existing into 2D grid structure attribute to hydrogen bonds between MeOH and free oxygen atom of the sulfonate group with another hydrogen atom of the carbon hydrogen from MeOH..3,Complex (8) and (13) were silimar polymer, so complex (11) and (2) were. Complex (12) was obtained by reaction of 2-pSO3H and ZnAc2·2H2O in methanol-water mixed solution under the condition of 320K,which belongs to Monoclinic, space group C2/c. A large number of strong hydrogen bonds O(4)-H(2W)...O(3)#2 2.707(2) ?,O(4) -H(1W)...O(2)#3 2.729(2) ? between uncoordinated oxygen atom of the sulfonate group and coordinated water molecule to construct 3D super molecular structure. The mixture was placed in a 23-mL Teflon-lined autoclave and heated at 130 oC for 72h. The autoclave was cooled over a period of 16 h at a rate of 5 oC h-1, and Complex (14) as yellow block crystals were collected by filtration. X-ray diffraction analysis indicates that complex 14 crystallizes in Monoclinic, space groupP2/n. The sulfonate group bridge Ag-O(1)-S(1)-O(3)-Ag (O(1)-S(1)-O(3) 112.84(13) o)each metal atom leading to a 1-D helix chain. Base on metal ion to metal ion, there are 1D channels(11.5 ?×8.5 ?) into 2D network structure with (3,6) grid.4,Complex (15) and (16) were synthesized by reaction of Zn(Ac)2·2H2O,Cd(Ac)2·2H2O , H2Saes and 4,4'-bipyridine in aqueous methanol (1:1,v:v), under the condition of different base to adjust the pH of solution,two novel one -dimensional coordination polymer。X-ray crystal structure of (15) thus obtained demonstrated that the Schiff-base ligand(Saes2-)acts as a tridentate moiety,two adjacent Zn II center are linked by 4,4'-bipyridine so it generates one–dimensional chains. Crystallizes (16), tridentate Schiff-base ligands acts as a monodentate coordinating Sulfonate groups oxygen, and the phenolato oxygen, imine nitrogen did not coordinated Cadmium. Two adjacent Cd II center are linked by 4,4'-bipy so it generates one–dimensional chains. intermolecular hydrogen bonds make great contributions to form 3D supermolicular structure in complex (15) and(16). BothÏ€-Ï€interaction of benzene and pyridine rings and a number of intermolecular hydrogen bonds make great contributions on stabilizing the solid state structures for (15) and (16). [Co(Saes)(H2O)(Bipy)]n·nH2O(17) was synthesized by reaction of Co(CH3COO)2·2H2O, H2Saes and 4,4'-bipy in aqueous methanol (1:1,v:v). Compound (17) The dimmers are packed in the solid state to give a hydrogen-bonded 3D structure. The layers are stacked one above the other in the third dimension, it results in the formation of a special 3D supramolecular MOF (Metal Organic Framework) with 1D channel.(18) was synthesized by reaction of Co(CH3COO)2·2H2O, H2Saes and 4,4'-bipy in aqueous methanol (1:1,v:v) Single crystal X-ray diffraction analysis indicates that the formation of a special 3D MOF (Metal Organic Framework) with 1D channe12.5×16.2?2(from metal ion to metal ion).5,Seven complexes of H2Sams have synthesized with different transition metal or adding the second ligands. As follow:(19)²⁵. Crystal X-ray diffraction analysis indicates that complex 19 crystallizes in cubic, space group Ia-3. Dinuclear nikel acts as each side of cubic cage, guest molecular cation [Na(H2O)6]+ located at the cubic cage13.44×13.44×13.44 ?3. The oxygen of sulfonic groups from each dinuclear nikel coordinated to potasium center constructed to 3D metal-organic frawork.The carboxylate group bridged adjacent metals (betweenCd(1) and Cd(2) 4.4 ?) and bridging ligands 4,4'-bipy forming 2D grid structure in complex (20) with (4,4) grid 4.4 ?×11.7 ?. Compound (21) is binuclear complex belongs to Triclinic, space group P-1,bothÏ€-Ï€interaction of benzene and benzene rings and intermolecular hydrogen bonds between complex molecular to construct three dimension supramolecular. X-ray crystallographic analysis indicate that the complex(22) belongs to monoclinic, space group C2/c. Intermolecular hydrogen bonds between complex molecular and free water and coordination water to form dimer. The X-ray crystallographic analysis indicate that the complex (23) crystallizes in monoclinic, space group P2(1)/n, hydrogen bonds of adjacent complex molecular and coordination water to form 1D super molecular structure. Binuclear copper complex (24) crystallizes in triclinic, space group P-1, Two Sams act as a tridentate moiety coordinated to two cooper center and form five coordination in a distorted pyramid geometry. Complex (25) was synthesized by the reaction of H2Sams and Cu(CH3COO)2·2H2O, which belongs to Triclinic, space group P-1. Intermolecular hydrogen bonds and interation of cooper and amino between complex(25) molecular to form 1D"ladder"superamolecular structure.In a word, whether the sulfonic groups coordinate to metal ion or not, and sulfonic compounds have been prepared through taking certain factors into account, such as the coordination nature of the metal ion and around the metal ion coordination enviroment,and the nature of replacement group (R). The sulfonic groups are expected to be excellent hydrogen bond acceptor and play an important role in hydrogen bonds forming. The hydrogen bonds are important in supramolecular force to govern the process of recognition and self-assembly of adjacent complex molecular. Superamolecular structure through intermolecular hydrogen bonds self-assembly enriched the study of the theories base on sulfonate groups.