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Synthese, Structures and Properties Study of Novel Coordination Polymers Base on Polycarboxylate and N-Heterocyclic Derivatives

Author: ChenHaiYan
Tutor: XiaoDongRong
School: Southwestern University
Course: Inorganic Chemistry
Keywords: Coordination Polymers Entangled Networks Hydrothermal Synthesis Crystal Structure Topology
CLC: O634
Type: Master's thesis
Year: 2012
Downloads: 141
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The aim of this thesis is to synthesize novel metal-organic coordination polymers which perhaps exhibit well photoluminescence, magnetic or gas adsorption/desorption properties, on the basis of flexible long-chain polycarboxylate, diverse N-heterocyclic derivatives of imidazole, triazol, or pyridyl ligands, and transition metal salts or alkaline-earth metal salts by hydrothermal techniques, to study the synthetic conditions and rules for these compounds, to analysize the topological types and entangled types, and to further explore the principle of self-assembley as well as the relationships between structures and properties for these new compounds.Thirty-one new metal-organic coordination polymers have been synthesized by hydrothermal reactions of polycarboxylate and metal ions in the presence of diverse N-heterocyclic derivatives of imidazole, triazol, or pyridyl ligands. Their structures were characterized by elemental analyses, ICP analyses, IR spectra, single-crystal X-ray diffraction analyses and X-ray powder diffraction (XRPD); while the thermal stabilities (TG), fluorescent and/or magnetic properties of these compounds have also been studied.1. Eighteen new metal-organic coordination networks with different types of entanglement have been hydrothermally synthesized by self-assembly of flexible long-chain polycarboxylate and transition metal salts or alkaline-earth metal salts in the presence of different N-heterocyclic derivatives, that are,[Mn4(sdba)4(bim)(H2O)4]-2H2O (1)[Ni(sdba)(bim)(H2O)2]-2H2O (2)[Co(sdba)(bim)(H2O)2]-2H2O (3)[Co3(sdba)2(Hsdba)2(2,2’-bpy)2](4) [Mn3(sdba)2(Hsdba)2(2,2’-bpy)2](5)[Mn2(sdba)2(btb)o.5(H20)](6)[Co(sdba)(bim)](7)[Cd(sdba)(bim)](8)[Cd(sdba)(bimp)](9)[Co2(odpa)(bim)2]-3H2O (10)[Zn(sdba)(Htpim)](11)[Cd2(sdba)2(Htpim)2(H2O)2]-5H2O (12)[Mn4(μ2-OH2)2(sdba)4(bpp)4](13)[Zn2(btec)(Htpim)2]·2H2O (14)[Ba(μ2-OH2)(sdba)(btb)0.5](15)[Ni2(stba)(bim)2(H2O)]·2H2O (16)[Ni2(bpda)2(bim)2]·H2O (17)[Cd(sdba)(H2O)](18)Compounds1-5are all uncommon (2D→2D) parallel interpenetrating arrays with coexistence of polyrotaxane and polycatenane, which are still quite rare in entangled systems up to now. Compound6represents the first example of2D polycatenated framework formed by1D quadruple chains, which could equally well be considered as formed by interconnected1D polyrotaxane columns involving unusual [3]rotaxane components. All of compounds7-10exhibit (2D→3D) interdigitated architectures assembled from different2D layers with helical structures. Compound11exhibits a novel (1D→3D) interdigitated architecture that is obtained from the self-assembly of1D tubelike structures. Compound12is the first case of interpenetration of two identical3D self-threading frameworks for entangled syatems, which represents the first entangled coordination polymer containing both interpenetration and self-threading feature. Compound13is a peculiar2D self-threading network containing unusual triflexural helical motifs, which can be rationalized as a6-connected2D36-hxl (hexagonal lattice) net with double edges. Compound14displays a new (2D→3D) polythreaded network that is obtained for the first time from the self-assembly from2D bilayer frameworks with dangling lateral arms. Compound15defines a new self-penetrating topology for binodal (5,12)-connected3D network, and represents the highest connected topology presently known for self-penetrating system. Compound16is a new4-connected3D self-penetrating network containing unusual entangled motifs, which are the interlock of Z-shaped chains and2D layers with helical structures. Compound17represents an unusual mode of interpenetration of two distinct3D frames both with CdSO4topology. Compound18exhibits an unusual twofold interpenetrating array with (3,6)-connected rutile topology.2. Seven porous metal-organic coordination polymers have been prepared by self-assembly of4,4’-sulfonyldibenzoic acid and alkaline-earth barium(II) ions in the presence of organic solvent molecules or assistant N-containing ligands, that are,[Ba(μ2-OH2)(sdba)(H2O)3]0.5H2O (19)[Ba(μ2-OH2)(sdba)(H2O)3]0.5ben-H2O (20)[Ba(μ2-OH2)(sdba)(H2O)3]0.5tolu-H2O (21)[Ba(μ2-OH2)(sdba)(H2O)3]-0.5(2,2’-bpy)-H2O (22)[Ba(μ2-OH2)(sdba)(H2O)3]-0.25bim-H2O (23)[Ba(μ2-OH2)(sdba)(H2O)3]0.5dfb-0.25H2O (24)[Ba(μ2-OH2)(sdba)(H2O)3]-3.5H2O (25)Compounds19-25are a series of3D porous coordination polymers exhibitting the same (2D→3D) interdigitated arrays assembled from unusual sidearm-containing2D bilayer motifs, which possess similar interlayer channels but encapsulate various species of guest molecules. These compounds show a series of variable parameters associated with the change of the species of guest molecules in their channels, including interlayer distance, dihedral angle of phenyl groups of sdba, dimension of channels and effective free volume, which well indicate the effect of guest-induced expanding and shrinking porous modulationm, and give a clue to a dynamic arrangement in this system. Furthermore, compounds19-25exhibits a series of intense and regular change of the luminescence behaviors.3. Two three-dimensional (3D) pillared metal-olsalazine complexes based on infinite rod-shaped secondary building units (SBUs) have been firstly isolated by hydrothermal reactions of anti-inflammatory drug olsalazine with a linear N-heterocyclic derivative1,4-bis(imidazol-l-yl)butane and transition metal salts, that are,[Co2(osa)(bim)(H2O)2](26)[Cd2(osa)(bim)(H2O)2](27)The variable-temperature magnetic data of compound26indicate a strong antiferromagnetic interaction between the CoⅡ ions. However, compound27displays good luminescent property.4. Four new metal-organic coordination supramolecular networks have been hydrothermally synthesized by using aromatic bidentate chelating ligand 1,10-phenanthroline with different polycarboxylate and transition metal salts, that are,[Cd(bqdc)(phen)](28)[Cd2(bctc)(phen)2(H2O)]·3H2O (29)[Mn2(cptc)(phen)3]-4.5H2O (30)[Zn(H2btc)(phen)2]+-H2btc-·3.5H2O (31)Compound28is comprised of2D(4,4) layers containning meso-helix motifs, which further connected by aromatic π-π stacking and C-H···O hydrogen-bonding interactions to form a3D supramolecular network. Compound29is composed of2D layers obtained by extending of quadrangle building blocks [Cd4(bctc)4(phen)4], which further connected by aromatic π-π stacking interactions to form a3D supramolecular network. Both compounds30and31exhibit0D structures of composition [Mn4(cptc)2(phen)6] and [Zn2(H2btc)2(phen)4]2+, respectively, which are further arranged with free molecules in spatial space to form3D supramolecular networks.

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