Syntheses,Structures And Properties Of Coordination Polymers Based On Multidentate Ligands

This work includes three parts:Firstly,we design and synthesize a tetradentate pyridine ligand,that is 1,1’-oxybis[3,5-di-4-pyridine]-benzene(L1).Thirteen compounds were synthesized by solvothermal method.Herein chiral and achiral compounds 1 and 2 were synthesized through the "one pot" method.Useage of V-type carboxylate ligands as co-ligand,five novel compounds 3-7 were synthesized.Then in presence of rigid carboxylate ligands,compounds 8-13 were synthesized.Second,seven novel coordination polymers 14-20 with novel frameworks and properties based on the nanosized tetradentate pyridine ligand N,N,N’,N’-tetrakis(4-(4-pyridine)-phenyl)biphenyl-4,4’-diamine(TPPDBA)via a solvothermal method.Finally,three compounds 21-23 were synthesized based on the tridentate acid ligand,5’-carboxyl-[1,1’:3’,1"-terphenyl]-4,4"-dicarboxylic acid(H3L).1.Syntheses,Structures,and Properties of Coordination polymers Based on 1,1 ’-oxybis[3,5-di-4-pyridine]-benzene(L1)Solvothermal reactions of 1,1’-oxybis[3,5-di-4-pyridine]-benzene(L1)with deprotonated 4,4’-oxydibenzoic acid(H2oba),4,4’-sulfonyldibenzoic acid(4,4’-H2sdb),4,4’-(hexafluoroisopropylidene)bis(benzoic acid)(H2hfipbb),1,4-benzenedicarboxylic acid(H2bdc),benzene-1,3,5-tricarboxylic acid(H3btc)in the presence of transition salts yielded thirteen complexes,namely,{[Co(L1)(oba)].H2O}n(1),{[Co5O2(L1)2(oba)3]·7DMF}n(2),{[Zn4(L1)2(4,4’-sdb)4(H2O)2]·10H2O}n(3),{[Zn2(L1)2(hfipbb)2(H2O)3]}n(4),{[Zn(-1)(oba)]-H2O}n(5),{[Cd2(L1)2(4,4’-sdb)2].2H20}n(6),{[Cd2(L1)(hfipbb)2(H2O)3]·2H2O}n(7),{[Zn(L1)(Hbdc)(bdc)0.5]·1.5H2O}n(8),{[Zn2(L1)(bdc)2(H2O)]-2H2O}n(9),{[Cd(L1)(bdc)(H2O)]·2H2O}n(10),{[Ni(Ll)(bdc)(H2O)]-H2O}n(11),{[CO3(L1)(btc)2(H2O)4]}n(12),{[Zn3(L1)(btc)2(H2O)4]}n(13).Compounds 1 and 2 have been synthesized by one-pot reactions.Compound 1 is a homochiral net with low connectivity,and compound 2 is an achiral 3D framework with high connectivity.They display quite different structures(low or high connectivity)and show significantly different physical properties.One contains coaxial double-stranded helical chains and another helical water chain and exhibits homochirality;the other with permanent porosity shows good affinity for hydrogen and carbon dioxide.For compounds 3-7,structural analysis reveals that the mixed ligands display versatile coordination modes to manage the metal ions to form homochiral,inclined polycatenation(1D-+2D),3-fold interpenetrating nets.However,the different coordinated modes,geometry and flexibility of ligands around metal ions result in subtle differences in the final architecture.Bulk materials for 1,3 and 5 have second-harmonic generation activities,approximately 0.3,0.4 and 0.8 times that of urea.In compound 8,L1 and bdc ligands link Zn centers to generate a two-dimensional(2D)sheet structure which is further connected by intermolecular hydrogen bonds to form a 3-fold interpenetrating 3D fsc array.Single crystal X-ray diffraction analysis reveals that compound 9 features a 3D self-interpenetrated network with {4.6.83.10}{4.63.82}{64.82} topology.For compounds 10 and 11,the binuclear metal secondary building unit(SBU)assembles with mixed ligands,L1 and bdc,to construct a 3D α-Po structure.Compounds 12 and 13 are isostructural and show 3-fold interpenetrated structures.The whole structure can thus be represented as a 2-nodal pte topology(with the Schlafli symbol {83}2{86}),which is only predicted by O’Keeffe,and is the first observation,to our knowledge,of pte topology in coordination polymers.2.Syntheses,Structures,and Properties of Coordination Polymers Based on N,N,N’,N’-tetrakis(4-(4-pyridine)-phenyl)biphenyl-4,4’-diamine(TPPDBA)Seven new coordination complexes,namely {[Zn2(TPPBDA)(HCO2-)4]·2H2O}n(14),{[Zn(TPPBDA)1/2(4,4’-sdb)]-2H20}n(15)and{[Zn(TPPBDA)1/2(oba).2DMF-2H20]}n(16),{[Cd2(TPPBDA)(oba)2]·4DMA-8H20}n(17),{[Cd(TPPBDA)(OH)2]·2H2O·4DMA}n(18),{[Cd(TPPBDA)1,2(1,3-tpdc)]·DMF}n(19),and{[Zn(TPPBDA)1/2(bpdc)]·3H2O·3DMF}n(20)have been synthesized by solvothermal reactions of TPPBDA with deprotonated 4,4’-H2sdb,H2oba,H2tpdc,or H2bpdc.In complex 14,the 2D ABAB parallel stacked network in which left-and right-handed helical chains coexist and array alternately(2Dchirai/2Dchirai→2Dachirai)makes 14 give rise to a new interesting 2D interwoven network.Complex 15 exhibits a 2D+2D→2D parallel interpenetrated network.For compound 16,the polycatenation among the 2D layer further extends the 2D net into a 3D framework.Compound 17 is a three dimensional net with 3D channels and meso-helical chains.The structural feature is that the arrangement of lattice DMA molecules is different in the different meso-helical channels.The material exhibits gas sorption properties for CO2,H2,and CH4.The adsorption selectivity of CO2/CH4 is calculated from the single-component isotherms using the dual-site Langmuir-Freundlich-based ideal adsorbed solution theory.In addition,the luminescent properties of the Cd-MOF in the solid state and suspension in different organic solvents have been investigated.For compounds 18-20,the coordination polymers built up of 4-connecting tetrahedral or planar-symmetric metal ions and TPPBDA ligands are precisely equivalent to the pts,bbf,and dia networks in which the interpentration forms are also different.In complex 18,the TPPBDA ligand connects four Cd(Ⅱ)cations in tetrahedral configuration.The Cd(Ⅱ)ion center coordinated by four TPPBDA ligands can be considered as square-planar nodes.Finally the ratio of tetrahedral(T)and square-planar(S)nodes is 1:1,which is the feature of pts.For compound 19,two carboxylates of the V-shape ligand tpdc2-adopt bidentate chelating coordination modes.There are two N atoms from two square-planar TPPBDA ligands occupying two vertices of the tetrahedral metal center,which results a bbf framework with the ratio(T:S)of 2:1.While linear linker bpdc2"takes place of V-shape ligand for compound 20,the TPPBDA ligand and the metal center are both in tetrahedral configuration,which constructs a dia net with the ratio of 2:0.The compounds all exhibit 4-connected nets,while there are some differences in the interpenetration forms.Compounds 18 and 20 are 4-fold interpenetrating pts and dia networks,respectively,while 19 is a 5-fold interpenetrating bbf framework.3.Syntheses,Structures,and Properties of Coordination Polymers Based on 5’-carboxyl-[1,1’:3’,1"-terphenyl]-4,4"-dicarboxylic acid(H3L)Three complexes,{[(Zn4O)1/2(Zn3-OH)1/2L3/2O1/4(H2O)5/2(NO2)1/2]·(H2O)4}n(21),{[Cd3L2(H2O)4]·(H2O)9·DMA}n(22),{[Co(HL)(4,4’-bibp)]}n(23),(H3L=5’-carboxyl-[1,1’:3’,1"-terphenyl]-4,4"-dicarboxylic acid,4,4’-bibp=4,4’-bisimidazolylbiphenyl,DMA=N,N-dimethylacetamide),have been synthesized under hydrothermal conditions.These compounds were characterized by elemental analysis,IR spectroscopy and X-ray single-crystal diffraction.Compound 21 reveals an unusual 3D structure with {4.52}{4.62}{42.52.68.83}{52.6}{53.65.82} topology based on Zn4O and Zn3-OH clusters.In compound 22,the H3L ligand assembles with Cd(NO3)2 to a 3D framework with sqc27 {4.62}2{42.610.83} topology.They are both three-dimensional frameworks containing one-dimensional channels.In compound 23,the HL2-anion and 4,4+-bibp both act as bidentate ligands and coordinate to Co cations to form a three dimensional 4-connected uninodal network.In addition,thermal stabilities for 21-23 and luminescent properties for 21-22 are also discussed in detail.