【作者】 王庆丽；

【导师】 牛云垠； 候红卫；

【作者基本信息】 郑州大学 ， 无机化学， 2007， 硕士

【摘要】 近年来，无机-有机杂化、微孔材料、分子材料和配位聚合物等是晶体工程学中的热点研究领域，由于配位聚合物具有迷人的拓扑结构，而且作为固体材料在非线性光学、分子选择、离子交换、催化、磁性等诸多方面具有广阔应用前景，所以成为当今化学、材料、生物、医学等领域研究的焦点。目前，国内外在金属卤／拟卤化物的配位化学研究上还不充分，这方面属于国内外晶体工程研究的前沿领域。本文运用分子设计和分子工程思想通过分子间的组装利用室温溶剂挥发法合成了八种结构新颖的原子簇及配位聚合物，并对它们的合成、结构、荧光性能、差热分析进行了系统的研究。首先，通过CuSCN、HgI₂和配体L1～L5自组装制备了5个配位聚合物{[Cu（SCN）₂（DMSO）₂（dpb）]（DMSO）}_n（1）、[Cu（SCN）₂（bpp）₂]_n（2）、[HgI₂（4-bpce）₂]（3）、[HgI₂（3-bpfob）]_n（4）、[CuSCN（4-bpfob）（H₂O）]_n（5）。配合物1、4形成了一维链状结构。2、5是CuSCN的二维网状结构，其中2是由配体桥联的具有棱形栅网状结构，而5是SCN^-桥联的含有双核金属大环的二维网状聚合物，在2、5的结构中配体均有两种构象存在。3是一个双核的二聚体，形成了13.025×12.663（?）²的孔径。其次，用CuI与配体L4～L6反应得到了3个原子簇聚合物[CuI（bpit）（THF）（H₂O）]_n（6），[CuI（3-bpfob）]_n（7）、[CuI（4-bpfob）（DMF）（CH₃CN）]_n（8）、三个结构中都含有Cu（I）中心和两个桥联碘原子形成了Cu（μ2-I）₂Cu菱面体，进而再分别与两个L4、L5、L6配体形成扩展成一维结构。其中7是一维双螺旋链状结构的聚合物，6和8均是一维双链结构聚合物。本文中所用到的配体更多还原

【Abstract】 Recently, inorganic-organic hybrid material, microporous material, monomolecular magnet and coordination polymers are the new research fields in the crystal engineering. The potentially applications of these compounds will be intensive in the fields of chemistry, material, medicines and biology.The construction of supramolecular polymeric networks is of great interest in recent years, not only for their intriguing architectures and topologies, but also for their potential properties as functional solid materials in NLO properties, molecular recognition, ion exchange, catalysis, magnetism etc.In this paper, novel cluster and coordination polymers were designed by treatment of metal halides/pseudohalides with organic ligands. We found it is rarely studied at present. Therefore, it belongs to the leading field of crystal engineering. Eight novel clusters and coordination complexes were obtained by treating six nitrogen-containing ligands with metal halides/pseudohalides via the method of solvent diffuse and solvent volatilization at room temperature. Furthmore, we have investigated their syntheses, structural analyses, and fluorescence properties.Firstly, through the assembly of CuSCN、HgI₂ and ligands L1～L5, coordination polymers 1～5 are generated: {[Cu（SCN）₂（DMSO）₂（dpb）] （DMSO）}_n （1）, [Cu（SCN）₂ （bpp）₂]_n（2）,[HgI₂（4-bpce）₃] （3）, [HgI₂（3-bpfob）]_n （4）, [CuSCN（4-bpfob）（H₂O）]_n（5）. 1～4 give one-dimensional chain complex, 2～5 are two-dimensional net coordination polymers. 2 is an arrangement of corrugated 2-D nets based on the （4, 4） topology, but 5 shows a 2-D network with binuclear metallamacrocycle by two bridging SCN^-. In the two coordination polymers 2 and 5, the ligands have two conformations. 3 is binuclear metallamacrocycle, two neighboring Hg（II） ions and two bridging ligands form an inner cavity with the size of 13.025×12.663A².Secondly, the reactions of CuI with L5～L6 ligands afford three new cluster coordination polymers [CuI（3-bpfob）]_n（6）, [CuI（4-bpfob）（DMF）（CH₃CN）]n （7）, [CuI（bpit） （THF）（H₂O）]_n （8）. 6,7 and 8 contain Cu（μ₂-I）₂Cu rhombohedron which is formed by two bridging iodides binding to two symmetry related Cu（I）. The Cu（μ₂-I）₂Cu units connecting two couples of bidentate 3-bpfob, 4-bpfob, bpit ligands form 1-D infinite chains. 6 is helical double-stranded 1-D coordination polymer, 7 and 8 are double-stranded 1-D coordination polymers.更多还原