【作者】 邓前军；

【导师】 梁宏； 黄可龙； 曾明华；

【作者基本信息】 中南大学 ， 应用化学， 2007， 博士

【摘要】 功能配位聚合物在光学、磁学、多孔、催化和手性等方面具有潜在的应用价值，基于含氮羧酸配体合成的功能配位聚合物材料目前已成为该领域最有吸引力的研究课题之一。本文通过选择几种含氮羧酸类型的配体和金属离子，依据晶体工程学原理，利用水热合成方法成功地合成了系列具有一维，二维和三维结构的配位聚合物，并对它们磁学、光学性质进行了调控和表征。初步总结了含氮羧酸配位聚合物的组装方法及其空间结构调控规律，探讨了部分配合物结构与性能的关系和规律。全文共分七章，第二、三、四章首次较详细地报道了1H-苯并咪唑-5-羧酸（Hbimc）配体的配位特点，合成了九种含bimc配体的配位聚合物，发现了其六种配位模式。第一章为前言部分，较系统地介绍了当前配位聚合物的主要研究内容、热点以及在磁学、光学、多孔材料方面的潜在应用，并说明了本课题选题意义和目前取得的研究成果。第二章利用bimc配体合成了三种锰、镍低维结构的稳定性高的配位聚合物，其中配合物[Mn（bimc）₂（H₂O）₂]·2H₂O（1）是一维线型链状结构，而配合物[Ni（bimc）₂]·H₂O（2）和Ni（bimc）₂（3）是两个因空间堆垛方式的不同而引起的互为超分子异构体的配位聚合物，两者都为二维（4，4′）层结构，配合物2是一种多孔材料，孔洞内装有溶剂水分子，去掉客体水分子后每个单元有效体积为750.1 （?）3（占总体积36.4％）。弱酸性的配体Hbimc表现了三种配位形式，a：μ₂-O2，N3、b：μ₂-（η₂-O1，O2），N3和c：μ₂-（η₂-O1，O2），N1。配合物1表现出顺磁行为，在低温时可能由链间金属磁耦合作用而产生了弱的反铁磁行为。配合物2表现反铁磁相互作用，主要来源于链间存在的反铁磁耦合作用，链内单核金属由桥联配体bimc连接的超交换作用非常小。第三章采用刚性的Hbimc配体和柔性的已二酸（H₂hex）配体与过渡金属（Mn、Co）盐合成了两种异质同晶的配位聚合物，配合物[Mn₂（bimc）₂（hex）]·2H₂O（4）和[Co₂（bimc）₂（hex）]·2H₂O（5）都是由含有二核四羧酸连接的桨轮形（paddle wheel）的SBU结构单元[M₂（OOCR）₄]，在小分子连接器的桥联下拓展成的二维层结构。配体bimc出现的配位模式是d类型：μ₃-O1，O2，N3。配合物4具有不同于一般的二核锰而类似于典型二核铜磁学性质，表现出反铁磁性，温度低于10 K时出现顺磁净质，实部磁化率(x_ac^′)对频率有较强的依赖性。配合物5具有自旋-轨道耦合现象，表现出较强的反铁磁性。第四章采用刚性的Hbimc作单一配体、以及分别和另外三种刚性的π共轭氮杂环配体混合与金属镉离子合成了四种低维结构的金属镉配位聚合物，其中配合物Cd（bimc）₂（6）和Cd（bimc）（phen）（H₂O）（7）是二维层状结构，而配合物Cd（bimc）（hq）（H₂O）（8）和[Cd₂（bimc）（bbp）₂（CH₃COO）]·H₂O（9）是一维链状结构。配体bimc出现了两种新的配位模式e和f类型，e：μ₃-（η₂-O1，O2′），N1，N3、f：μ₃-O1，N1，N3。配体bimc内由于存在含π共轭的芳香环，与d¹⁰金属镉形成的配合物具有荧光性质。当分别引入刚性的含π共轭的氮杂环的8-羟基喹啉、邻菲啰啉、2，6-二苯并咪唑毗啶时对配合物的荧光性质具有一定的影响，发出不同颜色的特征荧光，配合物6、7和8具有荧光寿命，其中尤以引入8-羟基喹啉的三元配合物8寿命较长。研究表明：刚性的含π共轭芳香环的Hbimc配体在构筑具有荧光性质的功能配位聚合物方面表现出了潜在的应用价值。第五章基于Hbimc和两种二羧酸混合配体与锰离子合成了二种只含二羧酸配体的锰配位聚合物。配合物Mn₃（imdc）₂（H₂O）₂（10）和Mn₅（suc）₄（OH）₂（11）是两种柱层式三维网状聚合物。其中配合物10是以二聚合体Mn（2）₂（imdc）₂（H₂O）₂连接成的层结构，在Mn（1）（imdc）₂（H₂O）为柱单元拓展下成的三维柱层结构。化合物11是以五核[Mn₅（OOCCH₂CH₂COO）₂（OH）₂]单元相互连接成层结构，以一个丁二酸配体柱单元拓展成的三维柱层结构。配合物10表现出较弱的反铁磁相互作用，主要是由二聚合体内两金属中心通过两个μ₂、η¹-COO^-桥联磁超交换作用的结果，而单聚体金属中心间的磁交换作用非常小。第六章利用三功能性的膦酸氨基甘氨酸（Hpmg）合成了两种三维网状结构的配位聚合物，其中配合物Pb₃[O₃PCH₂NHCH₂COO]₂·H₂O（12）内含有24-、10-、10-、8-四种成员环构成的通道体系，而配合物Cd（O₃PCH₂NH₂CH₂COO）₂（H₂O）₂（13）内含有12-、20-和20-三种成员环构成的通道体系，两配合物都具有类似于沸石结构的三维框架。本章配体pmg所表现的三种配位模式b、c、e，是以前文献从没报道过的。热稳定性分析表明配合物12沸石结构框架具有较高的热稳定性。研究表明：金属离子配位方式或离子半径的差别，反应条件中PH值的不同，可能会明显改变配体pmg去质子化方式，产生不同类型的阴离子和配位模式；三功能性的pmg配体在碱性较强的条件下易形成阴、阳两性离子[（O^-）₂OPCH₂NH₂⁺CH₂COO^-]。第七章对本论文工作进行了较全面地总结，归纳得到了结论，提出了展望。更多还原

【Abstract】 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 x_ac^′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 Mn^Ⅱions of the dimeric units of [Mn（2）₂（imdc）₂（H₂O）₂],however, the magnetic coupling between the Mn^Ⅱions 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.更多还原