Syntheses,Structures And Properties Of Coordination Polymers Based On Rigidity Pyridine Ligand And Triangle Flexible Carboxylate Ligand

This dissertation consists of three parts:Firstly,five coodination compounds based on 3,6-di-2-pyridyl-1,2,4,5-tetrazine?DPTZ?and Cu salts were synthesized in the presence of different acetonitrile/water ratios.Futher,we investigated their structures,mechanism and characteres.Secondly,we synthesized one flexible and symmetrical tris-?p-carboxyphenyl?-methane acid ligand?H₃TCOPM?and ten coodination compounds with novel structures and properties by hydrothermal method.We attained a novel MOF based on Zn6O cluster,and researched its adsorption and sensed small molecules.At the same time,fluorescences were investigated through some MOFs containg Cd.Thirdly,we synthesized one semi-flexible and symmetrical 3,5-bi?4-carboxy-phenoxy?-benzoic acid?H₃BCPBA?,and synthesized ten coodination compounds by hydrothermal method.We first synthesized a novel MOF based on Zn3O cluster with particular connection and researched its adsorption and sensing small molecules.The properties of other MOFs were investigated.1.Syntheses,structures and properties of coordination polymers based on contaning pyridine rigidity ligand Five coordination compounds were synthesized by the hydrothermal reaction ofDPTZ with Cu salts:[Cu₄?SO₄?₂?H₂O?₅?L²?₂]?1?,[Cu2SO4?H₂O?3?L2?]?2?,[Cu2??-CN?2?L1?]?3?,[Cu2SO4?bdc0.5?2?L2??H₂O?]?4??H₂bdc=p-phthalic acid?,[Cu?L3?2]?5?.Single-crystal X-ray diffraction analyses reveal that compound 1 crystallizes in the triclinic P1 space group and has one-dimensional?1D?structures with tetranuclear unit through sulfate.Compound 2 crystallizes in the orthorhombic crystal system of Pbca.Compound 3 crystallizes in the monoclinic space group C2/c.Compounds 2 and 3 own one-dimensional?1D?structures through sulfate or CN-.Complex 4 crystallizes in the triclinic P1 space group and shows a two-dimensional?2D?framework.Complex 5 is the known mononuclear compound.The results show:?1?if the ratio of solvent is 1:3,3 is obtained between 40-60?,whereas 1 yields between 80-120?.A mixture of 1 and 3 is obtained among 60-80?.The role of temperature in controlling forms can be rationalized as higher temperatures would afford more open ring crystal forms.?2?When the temperature is fixed?40-120??,the ratio of solvent vary from 1:2 to 3:1,interestingly,only 2 is attained.When the temperature is fixed at 120? and the ratio of solvent is 1:3,Cu?Ac?2·H₂O is substituted by CuSO4·6H₂O,it is surprising that 5 is obtained.This reaction process may provide a method to control the ring-cleavage of tetrazine of DPTZ step by step by the catalytic efffect of Cu salts.In addition,magnetic susceptibility measurements of compounds 1,2 and 4 exhibit strong antiferromagnetic coupling interaction.The magnetic behavior of 2 is similar to that of 1 through the N-C-O pathway,while the magnetic data of 4 can be reasonably analyzed through a model for a rectangle of local spin doublets with J1?through the diazine?and J2?across the monoatomic oxygen?.2.Syntheses,structures and properties of coordination compounds containing flexible tris?p-carboxyphenyl?methane acid ligand?H₃TCOPM?We synthesized a flexible tris?p-carboxyphenyl?methane acid ligand?H₃TCOPM?and nine coodination compounds with novel structures and properties by hydrothermal method:{[Zn₁₂??6-O?₂?TCOPM?4]·3H₂0·8NO₃·8DMF}n?6?,{[Zn₆??6-O??TCOPM?₂]·5H₂O·4NO₃·DMF}n?7?,{[Zn₄O?TCOPM?2?H₂O?₂]·8H₂O·3DMF}n?8?,{[Mn₃?TCOPM?₂?H₂O?2]}n?9?,{[Cd₃?TCOPM?₂?DMF??H₂O?₃]·3H₂O}n?10?,{[Cd₃?TCOPM?2?bipy?]·2H₂O·2DMF}n?11?,{[Cd4?TCOPM?₂?dpyb?₃?NO₂?₂·?H₂O?2]·5H₂O}n?12?,{[Cd₃?TCOPM?₂dpe]·6H₂O-DMF}n?13?{[Cd₃?TCOPM?₂bpe]·7H₂O·2DMF}n?14?{[Cd₃?TCOPM?₂pdp]·5H₂O·DMF}n?15?.Compound 6 with[Zn6??6-O?]cluster was synthesized firstly and crystallized in cubic space group Ia3?number 205?.Zn₆??6-O?clusters are linked by TCOPM^3-to generate the 3D framework with one dimensional?1D?channels,From the topology viewpoint,taking into consideration the TCOPM^3-ligand as 3-connected node and the Zn₆??6-O?cluster as 6-connected node,6???DMF can be considered to be a two nodal?3,6?connected 3D net with(6¹².8³)?6³?₂,the total topology type is pyr form of FeS2.6 takes up different amounts of N₂,H₂,CO₂,CH₄ and senses small molecules through fluorescence intensity response.Compound 7 crystallizes in the monoclinic crystal system of C2/c and exhibits a blue shifed fluorescenc which is due to the changes of the structures between 6 and 7.Compound 8 crystallizes in the orthorhombic crystal system of Pbcn and exhibits an unusual three-dimensional?3D?with?4-82??42-6??43·6·810·10?net topology framework based on Zn₄O cluster.Brunauer-Emmett-Teller?BET?surface area of compound 8 is 88.9 m2 g-1.9 crystallized in monoclinic space group C2/c and owned 3D structure with 1D channel,its topology is?43?2?46·6·8·84?and the topological type is tfz-d.Compound 10 crystallizes in the monoclinic P2/c space group with 2D structure and total potential solvent accessible void volume of 47.5%.Compound 11 is solved in monoclinic space group P2/c and posses a homogeneous channel with 3D structure with a total potential solvent accessible void volume of 29.9%.If omitting 4'4-bipy ligand,topological type of 11 is tfz-d which is the same to 9.Compound 12 crystallizes in the monoclinic C2/c space group with a total potential solvent accessible void volume of 15.5%.The Cdl acts as 8-conncting node,Cd₃ acts as 4-conncting node and TCOPM^3-are simplified as 3-connecting nodes,therefore,the topology can be described as a(6²³.8⁵)?6³?₂?6⁵.8?net.Compounds 10-12 all emit blue fluorescence.Compound 13 crystallizes in the triclinic P1 space group with 3D structure.TCOPM^3-adopts two coordinated mode:two carboxyl adopt bis?monodentate?bridging modes,one carboxyl adopts monatomic and chelating bridging modes.Auxiliary ligand does not affect their tops.Compouds 14 and 15 are smailar to 13.3.Syntheses,structures and properties of coordination compounds containing klexible 3,5-bis?4-carboxy-phenoxy?-benzoic acid?H₃BCPBA?We synthesized a flexible tris-?p-carboxyphenyl?-methane acid ligand?H₃TCOPM?and nine coodination compounds with novel structures and properties by hydrothermal method:{[Zn₅??3-OH?₄?BCPBA?2]·7H₂O·DMF}n?16?,{[Co?H₂BCPBA?₂?H₂O?₄]}n?17?,{{[Co?HBCPBA??bipy0.5?2·?H₂O?]}n?18?,{[Co₃?BCPBA?₂?dpe???4-H₂O?4]·4H₂O}n?19?,{[Co3?BCPBA?2?pdp?·??4-H₂O?₄]·2DMF}n?20?,{[Co₃?BCPBA?2?bpe?·?H₂O?2]·2DMF}n?21?,{[Co₂?HBCPBA?₂?bpp?·?H₂O?₂]·H₂O·2DMF}n?22?,{[Cd₃?BCPBA?₂.?DMA?₂·?H₂O?₅]·7H₂O·2DMA}n?23?,{[Cd₃?BCPBA?₂?bpp?·?DMF?₂]·10H₂O·3DMF}n?24?,{[Cd₃?BCPBA?₂?pdp?0.5?H₂O?2]·?pdp?0.5·H₂O]}n?25?.Compound 16 crystallizes in the monoclinic P1 space group with an unusual 3D?tfz-d?based on Zn₃O.16 obtained exhibits gas adsorption properties and senses of small molecules,exceptional thermal and chemical stabilities.Compound 17 is a zero-dimensional?0D?structure which is further connected by intermolecular hydrogen bonds to form a 3D supramolecular structure.Compound 18 is a two-dimensional?2D?sheet structure with 2D?2D two interpenetration frameworks which is further connected by intermolecular hydrogen bonds to form a 3D supramolecular structure.Compounds 19-21 are isostructural and possess three-dimensional?3D?networks with 3D?3D two interpenetration frameworks.Compound 22 which constructures by H₃TCOPM and bpp ligands link Co centers to generate a two-dimensional?2D?sheet structure which is further connected by intermolecular hydrogen bonds to form a 3D supramolecular structure.Compound 23 crystallizes in the monoclinic C2/c space group.23 consists of one and a half crystallographically independent Cd?II?ions,one BCPBA 3-ligand,and generates a three-dimensional?3D?sheet structure with one dimensional?1D?channels.Compound 24 crystallizes in the orthorhombic crystal system of Pna21 space group.24 consists of three crystallographically independent Cd?II?ions,two BCPBA^3-ligand,one bpp and generates a three-dimensional?3D?sheet structure.Compound 25 crystallizes in the monoclinic P21/c space group.25 consists of one and a half crystallographically independent Cd???ions,one BCPBA^3-ligand,one pdp and generates a three-dimensional?3D?sheet structure with one dimensional?ID?channels.H₃BCPBA ligand adopts different coordinated modes:one carboxylate adopts bis?monodentate?bridging modes,other two carboxylates adopt monodentate bridging modes.Trinuclear Cd cluster is formed through the connection of ?2-H₂O,and the angle of Cdl-?2-O-Cd₂ is 109.89°.25 possess three-dimensional?3D?networks with 3D?3D two interpenetration frameworks through the connection of BCPBA^3-and dpe.Schlafli is?4³?2(4⁶ 6¹⁸ 8⁴),and its kind is tfz-d.