【作者】 孟庆磊；

【导师】 梁福沛； 王利亚；

【作者基本信息】 广西师范大学 ， 无机化学， 2010， 硕士

【摘要】 由于金属羧酸配位聚合物具有结构多样性和潜在的磁性、催化、发光等性能而受到人们广泛关注。特别是芳香族多羧酸能够采用多种灵活方式与金属离子配位,常常被人们用来合成具有孔洞、磁性以及新颖结构的配位聚合物。本论文通过选用5-取代间苯二甲酸类及1,2,3-苯三酸、含氮辅助配体和过渡金属反应,系统研究取代基的差异对配位聚合物结构和性质的影响。在水热条件下合成了19个新型配位聚合物。然后对晶体结构进行了X-射线单晶衍射、红外光谱、元素分析、热分析、荧光和磁性等表征。1.利用5-甲氧基间苯二甲酸和醋酸锌、醋酸钴以及含氮辅助配体1,10-邻菲啰啉在水热条件下自组装得到了2个结构相似的一维链配合物[Zn(L)(phen)]n (1)和{[Co2(L)2(phen)2]·2H2O}n (2)。并对这些配合物的合成,结构和热稳定性以及配合物1的荧光性质进行了研究。2.利用5-甲基间苯二甲酸和5-叔丁基间苯二甲酸和柔性含氮辅助配体1,1’-(1,4-丁烷)双咪唑(bbi)在水热条件下设计构筑3个Cu(II)和Co(II)配位聚合物: [Cu2(mip)2(bbi)]n (3), {[Cu2(tbip)2(bbi)2(H2O)]·2H2O}n (4)和{[Co2(tbip)2(bbi)2]·2H2O}n (5)。未配位的取代基团对配合物的最终结构起着一定的作用。并对这些配合物的合成,结构和磁性以及其热稳定性进行了研究。3.利用5-硝基-1,2,3-苯三酸在水热条件下和不同的含氮辅助配体设计构筑了6个Cu(II), Co(II)和Ni(II)的配合物: [Cu3(nbta)2(bipy)2(H2O)2]?2H2O (6), [Cu3(nbta)2(bpp)2(H2O)2]?2H2O (7), [Co3(nbta)2(bipy)3(H2O)2]?2H2O (8), [Co3(nbta)2(bpp)2(H2O)2] (9), [Ni2(Hnbta)2(bipy)2(H2O)2] (10)和[Ni3(nbta)2(bpa)3(H2O)2]?2H2O (11)。并对这些配合物的合成,结构和磁性进行了研究。配合物的变温磁化率测量表明,配合物6, 7, 8和9的Cu(II)和Co(II)离子之间是反铁磁相互作用,而配合物10和11的Ni(II)离子之间存在铁磁相互作用。4.利用5-硝基-1,2,3-苯三酸和1,2,3-苯三酸在类似的水热条件下和不同的含氮辅助配体合成出8个Zn(II)和Cd(II)配位聚合物: {[Zn3(nbta)2(bipy)2(H2O)2]·2H2O}n (12), [Zn4(nbta)2(bpe)2(OH)2]n (13),{[Cd3(nbta)2(bipy)5(H2O)2]·6H2O}n (14), {[Cd3(nbta)2(bpe)2(H2O)2]·2H2O}n (15), {[Zn2(Hbta)2(bipy)2(H2O)2]·H2O}n (16), [Zn(bta)(Hbpe)]n (17), [Cd5(bta)2(Hbta)2(bipy)3(H2O)2]n (18)和{[Cd4(bta)2(bpe)2(H2O)4(OH)2]·2H2O}n (19)。配合物晶体结构研究表明,未配位吸电子基团(?NO2)在形成自穿插配位聚合物的过程中起着非常重要的作用。同时研究了配位聚合物的热稳定性和荧光性质。更多还原

【Abstract】 The rational design and construction of metal carboxylate coordination polymers is an interesting research field. The motive comes not only from the intriguing structural diversity but also from the demand for applications of functional materials in the fields of magnetism, catalysis, luminescence and so on. In particular, carboxylate ligands have been frequently empolyed in that their ability to engage in diverse bonding modes, allowing wide structural diversity and the tailoring of physical properties such as magnetism and porosity. Therefore, systematic studies have been carried out in this paper by reaction of transition metals, 5-substituted dicarboxylates or 1,2,3-benzenetricarboxylate and a series of N-donor ligands to investigate the influence of the difference substituents on the properties and construction of coordination frameworks. Nineteen coordination polymers have been synthesized on the basis of hydrothermal synthesis methods and characterized by X-ray single crystal analysis, IR spectra, elemental analysis, thermal analysis, fluorescence spectroscopy and magnetic susceptibility measurement.1. We reacted H2L with Zn(II) and Co(II) ions, then employed 1,10-phenanthroline as an auxiliary ligand, which feature two similar one-dimensional structures, namely [Zn(L)(phen)]n (1) and {[Co2(L)2(phen)2]·2H2O}n (2). We describe their syntheses, crystal structures, thermal stability as well as the luminescence of complex 1.2. We reacted H2mip and H2tbip with Cu(II) and Co(II), then employed 1,1’-(1,4-butanediyl)bis(imidazole) (bbi) as an auxiliary ligand, which feature three structures, namely [Cu2(mip)2(bbi)]n (3), {[Cu2(tbip)2(bbi)2(H2O)]·2H2O}n (4) and {[Co2(tbip)2(bbi)2]·2H2O}n (5). Variations in the molecular self-assembly are influenced by substituted group of the uncoordinated in the bridging ligands. Their syntheses, crystal structures, thermal stability and magnetic properties have also been investigated.3. Six Cu(II), Co(II) and Ni(II) complexes [Cu3(nbta)2(bipy)2(H2O)2]?2H2O (6), [Cu3(nbta)2(bpp)2(H2O)2]?2H2O (7), [Co3(nbta)2(bipy)3(H2O)2]?2H2O (8), [Co3(nbta)2(bpp)2(H2O)2] (9), [Ni2(Hnbta)2(bipy)2(H2O)2] (10) and [Ni3(nbta)2(bpa)3(H2O)2]?2H2O (11) were prepared through hydrothermal reactions from H3nbta. We report the synthesis, structural characterization, and magnetic investigation of these complexes. Magnetic studies reveal that there are antiferromagnetic interactions between the transition metal ions in the polymeric CuII (6 and 7) and CoII complexes (8 and 9), while ferromagnetic interactions in the polymeric NiII complexes (10 and 11).4. Eight Zn(II) and Cd(II) coordination complexes, {[Zn3(nbta)2(bipy)2(H2O)2]·2H2O}n (12), [Zn4(nbta)2(bpe)2(OH)2]n (13), {[Cd3(nbta)2(bipy)5(H2O)2]·6H2O}n (14), {[Cd3(nbta)2(bpe)2(H2O)2]·2H2O}n (15), {[Zn2(Hbta)2(bipy)2(H2O)2]·H2O}n (16), [Zn(bta)(Hbpe)]n (17), [Cd5(bta)2(Hbta)2(bipy)3(H2O)2]n (18) and {[Cd4(bta)2(bpe)2(H2O)4(OH)2]·2H2O}n (19) were prepared through hydrothermal reactions from H3nbta or H3bta. The results reveal that the existence of electron-withdrawing–NO2 group in such a tricarboxyl building block plays a critical role in structural direction of the self-penetrating coordination frameworks. The thermal and photoluminescent properties of these complexes have also been investigated.更多还原