The Study Of Coordination Polymers Constructed From Aromatic Carboxylic Acids And Flexible N-donor Ligands

In this work, a series of coordination polymers (CPs) constructed from aromaticcarboxylic acids, flexible N-donor ligands and transition metal ions have beensynthesized under hydrothermal conditions and characterized by the single crystalX-ray diffraction, elemental analyses, infrared spectra (IR), powder X-ray diffractionspectra (PXRD) and thermogravimetric analysis (TGA). The synthesis conditions,topologies of crystal structures, influences of structural features of organic ligands onthe structures of final products have been investigated in detail. In addition, theluminescent properties and diffuse reflectivity spectra have also been studiedpreliminarily.1. Eight structurally related salicylate ligands (H2L1=salicylic acid, H2L2=3-methylsalicylic acid, H2L3=4-methylsalicylic acid, H2L4=4-chlorosalicylic acid,H2L5=5-chlorosalicylic acid, H2L6=5-bromosalicylic acid, H2L7=5-nitrosalicylicacid and H3L8=5-sulfosalicylic acid) and the flexible N-donor ligand (biim-4=1,1’-(1,4-butanediyl)bis(imidazole)) were used as organic ligands, and thirteen newZn(II)/Cd(II)-containing complexes, namely,[Zn2(L1)2(biim-4)(H2O)](1),[Cd(HL1)2(biim-4)](2),[Cd(HL2)2(biim-4)](3),[Cd(HL3)2(biim-4)](4),[Zn2(L4)2(biim-4)(H2O)](5),[Cd(HL4)2(biim-4)](6),[Zn2(L5)2(biim-4)(H2O)](7),[Cd2(HL5)4(biim-4)3]2H2O (8),[Zn2(L6)2(biim-4)(H2O)](9),[Cd(HL6)2(biim-4)](10),[Zn2(L7)2(biim-4)2]·H2O (11),[Cd2(L7)2(biim-4)2(H2O)]·H2O (12), and[Zn(HL8)(biim-4)]·0.5H2O (13), have been synthesized under hydrothermalconditions. Compounds1and5are isomorphous, and show the same3-connected103-ths net. Compound2possesses a meso-helical chain structure. Compound3shows a zero-dimensional (0D) dimeric molecular structure, which is linked by π–πinteractions into a two-dimensional (2D) supramolecular assembly. Compounds4and6exhibit similar one-dimensional (1D) chains, which are extended into different2Dsupramolecular layers via C–H···O and C–H···Cl hydrogen-bonding interactions,respectively. Compound9is isomorphous with7, and displays a typicalthree-dimensional (3D) diamond framework. Compound8shows an unusual2D→3Dpolythreading array. Compound10furnishes a2D supramolecular44-sql networkformed by C–H···Br hydrogen-bonding interactions. Compounds11and12exhibitbinodal (4,4)-connected3D frameworks with (4·53·72)(4·52·83) and(42·62·82)(42·6·82·10) topologies, respectively. Compound13has a3D4-fold interpenetrating diamond framework. The effects of the organic anions and centralmetal ions on the structures of products have been discussed in detail. Moreover, theluminescent behaviors of1-13have also been investigated.2. The combination of3,5-dinitrosalicylic acid (H2dns) and nine flexiblebis(triazole) ligands (L1=1,2-bis(1,2,4-triazol-1-yl)ethane, L2=1,3-bis(1,2,4-triazol-1-yl)propane, L3=1,4-bis(1,2,4-triazol-1-yl)butane, L4=1,5-bis(1,2,4-triazol-1-yl)pentane, L5=1,5-bis(1,3,4-triazol-1-yl)pentane, L6=1,6-bis(1,2,4-triazol-1-yl)hexane, L7=1,10-bis(1,2,4-triazol-1-yl)decane, L8=1,4-bis((1H-1,2,4-triazol-1-yl)methyl)benzene and L9=1,1’-(2,2’-oxybis(ethane-2,1-diyl))bis(1H-1,2,4-triazole)) in the presence of Cu(II) andCd(II) ions provides eleven complexes, which are formulated as[Cu4(dns)4(L1)2(H2O)]·2H2O (14),[Cu4(dns)4(L2)2(H2O)](15),[Cu2(dns)2(L3)(H2O)](16),[Cu2(dns)2(L4)(H2O)](17),[Cu5(dns)4(OH)2(L5)2(H2O)3]·H2O (18),[Cu(dns)(L6)](19),[Cu2(dns)2(L7)](20),[Cu(dns)(L8)]·0.5H2O (21),[Cd2(dns)2(L1)(H2O)2](22),[Cd2(dns)2(L7)3](23) and [Cd4(dns)4(L9)4](24).Compounds14and17possess one-dimensional (1D) double chains. Compounds15,16and18show2D44networks. Compound19furnishes a3D uninodaleight-connected self-penetrating framework with (42068) topology. Compound20reveals a2D2-fold interpenetrating44-sql network. Compounds21and22feature2Dundulated layers. Compound23shows a1D chain. Compound24furnishes a discretetetranuclear cluster. The influence of the bis(triazole) ligands on the structures ofcompounds are discussed in detail. Furthermore, the diffuse reflectivity spectra ofcompounds have also been studied at room temperature.3. Eleven Zn(II)/Cd(II)-containing coordination polymers incorporating bothflexible4-substituted bis(1,2,4-triazole) ligands (L10=1,2-bis(2-(4H-1,2,4-triazol-4-yl)phenoxy)ethane, L11=1,2-bis(3-(4H-1,2,4-triazol-4-yl)phenoxy)ethane and L12=1,2-bis(4-(4H-1,2,4-triazol-4-yl)phenoxy)ethane) and polycarboxylate anions(o-H2BDC=phthalic acid, m-H2BDC=isophthalic acid, p-H2BDC=terephthalicacid, and H4BTEC=pyromellitic acid), namely,[Zn(L1)(o-BDC)]·1.5H2O (25),[Zn(L1)(m-BDC)](26),[Cd2(L1)(BTEC)]·H2O (27),[Zn(L2)(m-BDC)]·1.25H2O (28),[Zn(L2)(p-BDC)]·4H2O (29),[Cd(L2)(p-BDC)]·H2O (30),[Zn2(L2)(BTEC)](31),[Zn(L3)(m-BDC)]·3.5H2O (32),[Zn2(L3)(p-BDC)2]·2H2O (33),[Zn2(L3)2(BTEC)]·2H2O (34) and [Cd2(L3)2(BTEC)](35), have been prepared andidentified by physical measurements. Compound25possesses a layered structure.Compound26shows1D chains. Weak π-π intermolecular stackings further join thesechains into a2D supramolecular layered structure. Compound27displays a3D(4,8)-connected (32·42·52)(34·48·512·64) net. Compound28consists of two interlocked single-wall metal-organic nanotubes (SWMONTs) with both polyrotaxane andpolycatenane characters. Compound29exhibits a3D5-fold interpenetrating diamondmotif. Compound30furnishes a3D α-Po net. Compound31reveals a3D(4,6)-connected net with (43·63)(46·66·83) topology. Compound32features a2D4-connected network with (65·8) topology. Compound33shows a3D3-foldinterpenetrating α-Po net. Compounds34and35display3D (4,4)-connected nets withthe same (64·7·8)(62·84) topology. The effects of the4-substituted bis(1,2,4-triazole)ligands, aromatic polycarboxylate anions, and metals ions on the frameworkassemblies have been discussed. Besides, the solid-state luminescent of compounds25-35and fluorescent properties of compounds2831in various solvent suspensionswere investigated at room temperature.