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Hydrothermal Synthesis,Crystal Structure And Properties Of Some Functional Coordination Polymers Based Carboxylic Acid With N Donor

Posted on:2008-02-08Degree:DoctorType:Dissertation
Country:ChinaCandidate:Q J DengFull Text:PDF
GTID:1101360215998941Subject:Applied Chemistry
Abstract/Summary:PDF Full Text Request
Functional coordination polymers have potential applications in theareas of luminescence, magnetism, porosity, catalysis, conductivityand chirality etc, The carboxylic acids with N donor as bridged ligandsconstruct directionally functional coordination polymers is one of themost attractive topics of current researches.In this manuscript, we use some carboxylic with acid N donorligands and metal ions to synthesized a series of 1D, 2D, 3D coordinationpolymers with hydrothermal synthetic methods in terms ofcrystallography theory and further studied their magnetism andfluorescence. It is also investigated how to controlled assembly thestucture and desired properties coordination polymers, moreover, therelation between structure and property is discussed.This thesis is divided into seven chapters, and in the former threechapters we first detailedly report coordination characteristic of1H-benzimidazole-5-carboxylic acid(Hbimc) with nine complexes andsix coordination modes.In the first chapter, the main studied content, topics and potentialapplications in magnetism, luminescence and porosity of coordinationpolymers are systemically introduced, as well as the research significanceand the results of this thesis.In the second chapter, three low dimensional coordination polymerswere obtained by hydrothermal reaction with high thermal stability.Thecomplex of [Mn(bimc)2(H2O)2]·(H2O)2(1) exhibits 1D linear chainsturcture, and two surpramolecular isomerisms of [Ni(bimc)2]·H2O(2)and [Ni(bimc)2] (3) are 2D (4, 4') layer architecture. Complex 2 is amicroporous material comtaining neutral guest water molecules with avoid volume of 750.1 (?)3 (36.4%) throwing off water. Bimc ligandexhibits three bridging coordinational modes of a: (μ2-O2, N3), b: [μ2--(η2-O1, O2), N3] and c: (μ2-(η2-O1, O2'), N1). Complex 1 showsparamagnetic property, and in the lower temperature weak antiferromagnetism by possibly Mn(Ⅱ) ions coupling interaction betweeninterchains. There is weak antiferromagnetic coupling interaction in thecomplex 2 between Ni(Ⅱ) ions through the bimc bridging, and also thereis partly weak ferromagnetic property.In the third chapter, two heterogeneous isostructural coordinationpolymers were synthesized containing rigid bimc, flexible hex andtranstion metals(Mn, Co). Both [Mn2(bimc)2(hex)]·2H2O(4) and[Co2(bimc)2(hex)]·2H2O(5) are 2D structure via bridging paddle wheelSBU [M2(OOCR)4] by small molecule linker. Bimc ligand exhibits anew coordinational modes of d:μ3-O1, O2, N3. Complex 4 showsantiferromagnetism like dinuclear copper complex and the presence ofparamagnetic impurities below 10 K, and in-phase susceptibility xac′exhibits a frequency-independent peak, and complex 5 shows stronglyantiferromagnetism with spin-orbit coupling.In the fourth chapter, four low dimensional cadmium coordinationpolymers were obtained with rigid bimc and threeπ-conjugate with Nligands. The complexes of Cd(bimc)2(6), Cd(bimc)(phen)(H2O)(7)belong to 2D layer architecture, and Cd(bimc)(hq)(H2O)(8),Cd2(bimc)(Hbbp)2(CH3COO)(H2O)(9) exhibit 1D chain sturcture. Thesecond ligand and void obstruct can influence the coordination mode ofbimc to behave two novel forms of e:μ3-(η2-O1,O2'), N1, N3 and f;μ3-O1, N1, N3. Complexes containing bimc and d10 metals showfluorescence owing toπ-conjugate aroma ring in ligand bimc, andComplex 6, 7, 8 exhibit fluorescence releasing out differ tinctorial lightwith fluorescence life, and complex 8 behave bigger life. Result indicate:the rigid ligand Hbimc containingπ-conjugate aroma ring in theassembling functional coordination polymers with fluorescence exhibitspotential applications.In the fifth chapter, two manganeses complexes were synthesizedonly containing dicarboxylic acid based on mixed ligand of Hbimc anddicarboxylic acids. Two three-dimensional manganese coordinationpolymers of [Mn2(imdc)2(H2O)2]n(10) and [Mn5(hex)2(OH)2]n(11) are 3Dnetworks containing pillared layers, complex 10 consists of dimeric[Mn(2)2(imdc)2(H2O)2] layers and [Mn(1)(imdc)2(H2O)] pillars, and complex 11 consists of [Mn5(OOCCH2CH2COO)2(OH)2] layers anddeprotonated succinic acid pillars. Complex 10 shows a weakantiferromagnetic coupling interaction between theμ2,η1-COO-bridging MnⅡions of the dimeric units of [Mn(2)2(imdc)2(H2O)2],however, the magnetic coupling between the MnⅡions of[Mn(1)(imdc)2(H2O)] units is little.In the sixth chapter, two coordination polymers with 3D networkswere obtained in hydrothermal reaction. Both of Pb3[O3PCH2NHCH2COO]2·0.5H2O(12) and Cd(O3PCH2NH2CH2COO)2(H2O)2(13) containcomplex channel systems constituted of 24-, 10-, 10-, 8-membered ringsand 12-, 20-and 20-membered rings, respectively, and are analogous tozeolite-type frameworks. The three coordination modes of pmg are notreported in the references. Result indicate: coordination fashions andradius of metal ions and the pH value of the reaction system can changedeprotonated mode of the ligand pmg to result different types of ions andcoordination modes, as well as trifunctional pmg reveals easily zwitterionof [-2O3PCH2NH2+CH2COO-] in the strong alkali. Complex 12 show highthermal stability.In the last chapter, a briefly conclusion on this work has beenviewed and an outlook have been viewed.
Keywords/Search Tags:functional coordination polymer, crystal structure, carboxylic acid with N donor ligand, magnetism, fluorescence
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