节点文献
基于手性氨基酸衍生物配体配合物的合成及性能表征
Synthesis, Characterization and Properties of the Complexes Constructed from Chiral Amino Acid Derivates
【作者】 何蓉；
【导师】 宋会花；
【作者基本信息】 河北师范大学 ， 无机化学， 2010， 硕士
【摘要】 近年来,金属-有机框架材料（MOFs）的设计和合成以其结构的多样性及在催化、发光等功能材料领域的广泛的用途愈来愈受到人们的重视。本文在对手性的金属有机配位聚合物进行综述的基础上,设计合成了一系列基于手性氨基酸衍生物配合物,并对其结构和性能进行了研究。本论文的主要研究内容如下:（1）以对甲苯磺酰-L-谷氨酸为配体,合成了11种新型配合物: {[M （tsgluO）（2,4’-bipy）2（H2O）2]·5H2O}n （M= Ni,1; Co,2）, {M（tsgluO）（4,4’-bipy）·0.5H2O}n （M= Ni,3; Co,4）, {[Cu（tsgluO）（H2O）]2·3H2O}n （5）, {Cu（tsgluO）（2,2’-bipy）}n （6）, {Zn（imi）（H2O）（tsgluO）}n （7）, {[Zn（2,4’-bipy）（H2O）]（tsgluO）}n （8）, [Mn（4,4’-bipy）2（H2O）4]（HtsgluO）2·2H2O （9）, {Zn（bpp）2（tsgluO-Me）2}n （10）, {Zn（bpp）（tsgluO-Me）2}n （11）（H2tsgluO = （+）-N-对甲苯磺酰-L-谷氨酸;bipy =联吡啶;imi=咪唑;bpp=1,3-联（4-吡啶基）丙烷）。用元素分析、红外光谱、热重分析、X-射线单晶衍射进行了表征,并对配合物1-5的磁性、配合物7-11的荧光性质及配合物5的催化性能进行了研究。此外,还意外获得化合物tsgluO-Me2 （12）的单晶结构。配合物1和2同构,它们都是Cc非心空间群,具有一维链状结构,链与链之间进一步通过π-π堆积和氢键作用连接成三维超分子结构。配合物3是P21手性空间群,具有二维层状结构,层与层间通过氢键作用连接成三维超分子结构。配合物4是P-1中心空间群,具有二维层状结构,层与层间通过π-π堆积和氢键作用连接成具有一维隧道的三维超分子结构,隧道中有晶格水分子填充。配合物5是P21手性空间群,由双核“浆轮”单元构成的一维链状配合物,链间再通过极弱的π-π堆积和分子间氢键作用连接成具有一维通道的三维网状结构,通道中占据着客体水分子。配合物6是P212121手性空间群,具有一维双链结构。配合物7是P21手性空间群,具有一维双链结构,进一步通过氢键作用形成二维超分子结构。配合物8是P21/c中心空间群,具有一维单链结构。配合物9是P-1中心空间群,包含有[Mn（4,4’-bipy）2（H2O）4]2+阳离子和HL-阴离子两部分,它们之间通过π-π堆积、氢键以及范德华力作用形成二维超分子结构。配合物10是P-1中心空间群,具有双链结构,并通过氢键作用形成具有一维通道无客体分子占据的二维超分子结构。配合物11是P-1中心空间群,具有一维单链结构。化合物12是P-1中心空间群,由配体tsgluO-H2和甲醇酯化得到的小分子化合物。配合物1-4中存在非常弱的反铁磁相互作用,配合物5中存在双核铜的反铁磁耦合作用。配合物7-11都表现出较强的荧光。配合物5在苯乙烯不对称环氧化反应中,具有较好的催化活性。（2）以邻苯二甲酰-L-缬氨酸为配体,构筑了7种新型配合物: [Mn（phen）2（HL）2·3.5H2O] （13）, [Mn（phen）2（phth）（H2O）·4H2O] （14）, {Cu（phen）（H2O）（phth）·CH3OH}n （15）, {[Cu（2,2’-bipy）（H2O）]（phth）·3.5H2O}n （16）, {Zn（phen）（phth）（H2O）·1.125H2O}n （17）, {[M（4,4’-bipy）（H2O）2]（phth）·2H2O}n （M= Zn,18; Mn,19）（H2L =邻苯二甲酰-L-缬氨酸;phth2- =邻苯二甲酸根离子;bipy =联吡啶;phen = 1, 10-邻菲啰啉），用元素分析、红外光谱、热重分析、X-射线单晶衍射进行了表征,并对配合物14,15,16和19的磁性进行了研究。配合物13具有C2/c中心空间群,是小分子化合物,通过π-π堆积和氢键作用形成具有一维通道的三维网状结构,通道中占据着客体水分子。很遗憾的是,配合物14-19中配体邻苯二甲酰-L-缬氨酸进行了水解,最后形成了phth2-的配合物。配合物14具有P21/c中心空间群,是小分子化合物,仅通过π-π堆积作用形成具有一维通道的链状结构。配合物15是Pbcm中心空间群,具有一维链结构,通过氢键作用形成具有客体分子占据的纳米孔道二维网状结构。配合物16是P21/c中心空间群,具有一维链结构,通过π-π堆积和氢键作用形成三维超分子结构。配合物17是P21/c中心空间群,具有一维螺旋链结构,并通过弱的π-π堆积作用形成二维网格结构。配合物18和19是同构的,金属中心分别为锌和锰,都是P2/c中心空间群,都具有二维层状结构,并通过氢键作用形成三维超分子结构。磁性研究表明,配合物14,15,16和19具有反铁磁相互作用。
【Abstract】 In recent years, the design and synthesis of metal-organic frameworks （MOFs） have afforded a great deal of interest because of their various structures and extensive applications in the filed of functional materials such as catalysis, luminescence and etc. This paper summarizes the research advances of chiral coordination polymers. A series of coordination polymers constructed by chiral amino derivatives have been synthesized, and their crystal structures and properties were determined. In this paper, the main results are as follows:First, eleven coordination compounds constructed by （+）-N-Tosyl-L-glutamic acid: {[M （tsgluO）（2,4’-bipy）2（H2O）2]·5H2O}n （M= Ni,1; Co,2）, {M（tsgluO）（4,4’-bipy）·0.5H2O}n （M= Ni,3; Co,4）, {[Cu（tsgluO）（H2O）]2·3H2O}n （5）, {Cu（tsgluO）（2,2’-bipy）}n （6）, {Zn（imi）（H2O）（tsgluO）}n （7）, {[Zn（2,4’-bipy）（H2O）]（tsgluO）}n （8）, [Mn（4,4’-bipy）2（H2O）4]（HtsgluO）2·2H2O （9）, {Zn（bpp）2（tsgluO-Me）2}n （10）, {Zn（bpp）（tsgluO-Me）2}n （11） （H2tsgluO = （+）-N-Tosyl-L-glutamic acid, bipy= bipyridine, imi= imidazole, bpp= 1,3-bis（4-pyridyl）propane） have been synthesized and characterized by X-ray diffraction analysis, elemental analysis, IR, thermal analysis, and their fluorescent and magnetic properties and asymmetric catalysis were also studied. Unexpectedly, tsgluO-Me2 （12） was obtained.Compounds 1 and 2 are isostructural and crystallize in the acentric monoclinic space group Cc, forming the same 1D chain structures. The chains are further connected byπ-πstacking and hydrogen bonds interactions to form 3D supramolecular network. Compound 3 shows the chiral space group P21, forming a homochiral 2D architecture, which is further connected by hydrogen bonding interactions to form three-dimensional supramolecular network. Compound 4 crystallizes in the space group P-1 and is composed of binuclear [Co2O6N2]n4- units, which presents a 2D bilayer framework and is further connected by hydrogen bonding andπ-πpacking interactions to form three-dimensional supramolecular network containing one-dimensional channels with lattice water molecules. Compound 5 crystallizes in the space group P21 and contains a paddle-wheel dicopper（II） structure, which is featuring 1D double chains. The chains are further self-assembled through the non-covalent interactions of weakπ-πstacking and hydrogen bond to form pseudo-3D supramolecular structures with 1D channels, where the guest water molecules are located. Compounds 6 crystallizes in the chiral space group P212121 and is giving ladder-like 1D double chains. Compounds 7 crystallizes in the chiral space group P21 and shows ladder-like 1D double chains. The double chains are further connected by hydrogen bonding to form two-dimensional supramolecular network. Compound 8 crystallizes in the space group P21/c and is giving a 1D single chain, which is self-assembled to form 2D supramolecular structures through hydrogen bonding interactions. Compound 9 crystallizes in the space group P-1 and is connected byπ-πstacking and hydrogen bonding interactions to form 3D supramolecular network. Compounds 10 and 11 crystallize in the space group P-1 and display 1D chain structures. What different is that compound 10 is a 1D bpp-connected Zn–bpp–Zn double chain and further hydrogen-bonded into 2D networks. The formation of the tsgluO-Me2 moiety in compound 12 results from an in situ esterification reaction between tsgluO-H2 and methanol and is driven by an excess of methanol and anhydrous conditions. Additionally, magnetic properties study indicates that compounds 1-4 show weak antiferromagnetic interactions. Compound 5 shows antiferromagnetic interactions between the Cu（II） centers of each dicopper unit. Compounds 7-11 show intense fluorescence at room temperature. Catalytic study indicates that compound 5 shows well-catalytic properties.Second, seven coordination compounds constructed by phthalyl-L-valine acid: [Mn（phen）2（HL）2·3.5H2O] （13）, [Mn（phen）2（phth）（H2O）·4H2O] （14）, {Cu（phen）（H2O）（phth）·CH3OH}n （15）, {[Cu（2,2’-bipy）（H2O）]（phth）·3.5H2O}n （16）, {Zn（phen）（phth）（H2O）·1.125H2O}n （17）, {[M（4,4’-bipy）（H2O）2]（phth）·2H2O}n （M= Zn,18; Mn,19） （H2L = phthalyl-L-valine acid, H2phth = phthalic acid, bipy = bipyridine, phen = 1,10-phenanthroline） have been synthesized and characterized by X-ray diffraction analysis, elemental analysis, IR, thermal analysis, and their fluorescent and magnetic properties.Compound 13 crystallizes in the space group C2/c and is further connected byπ-πstacking and hydrogen bonds interactions to form 3D supramolecular network containing 1D channels with lattice water molecules. Compound 14 crystallizes in the space group P21/c and is further extended into 1D chain throughπ-πstacking. Compound 15 crystallizes in the space group Pbcm and exhibits a 1D chain structure, which is further hydrogen-bonded into 2D networks. But unfortunately, the phthalyl-L-valine acid decomposed into the phth2- ligand in the formation of compounds 16, 17, 18 and 19. Compound 16 crystallizes in the space group P21/c and shows a 1D chain structure, which is further extended into 3D supramolecular network throughπ-πstacking and hydrogen bonds interactions. Compound 17 crystallizes in the space group P21/c and is a 1D helix chain structure, which is further linked into 2D networks throughπ-πstacking. Compounds 18 and 19 are isostructural and crystallize in the space group P2/c. They exhibit the same 2D layers, which are further connected by hydrogen bonds interactions to form 3D supramolecular network. Magnetic properties study indicates that compounds 14, 15, 16 and 19 show weak antiferromagnetic interactions.
【Key words】 coordination polymer； chiral amino derivatives； crystal structure； fluorescent properties； magnetic properties；