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基于(4-羧基苯基)(4-(2-羧基苯基)苄基)醚的配合物的合成及结构
Syntheses and Structures of Coordination Compounds Based on (4-carboxyphenyl)(4-(2-carboxyphenyl)benzyl) Ether
【作者】 张莹;
【导师】 李斌;
【作者基本信息】 东北师范大学 , 无机化学, 2013, 硕士
【摘要】 本论文合成了未见报道过的14种基于(4-羧基苯基)(4-(2-羧基苯基)苄基)醚(H2L)和3种含氮中性配体(biim-4=1,4-二(1-咪唑基)丁烷、BIE=2,2’-二(1-咪唑基)乙醚和phen=1,10-二氮杂菲)的新型配位聚合物{[Zn3(L)3(biim-4)2]·H2O (1)、[Cd(L)(H2O)(biim-4)0.5](2)、[Zn(L)(BIE)](3)、[Co(L)(BIE)](4)、[Cd(L)(BIE)](5)、[Ni(L)(BIE)](6)、[Ni(L)(phen)]·H2O (7)、[Co(L)(phen)]·H2O (8)、[Co(HL)2(phen)2]·3H2O (9)、[Cd(L)(H2O)(phen)](10)、[Co(L)(H2O)(phen)](11)、[Cd(L)(phen)2](12)、[Pb(L)](13)和[Pb(L)(phen)]·H2O (14)}。通过单晶X-射线衍射测定了它们的晶体结构。化合物1具有罕见的三维4,5-两节点(43·62·8)(45·5·64)拓扑结构。化合物2具有一维链状结构,这些聚合链通过π-π作用堆积成三维超分子结构。化合物3-6是同构的,拥有相似的二维层状结构。化合物7和8具有零维结构,配合物分子通过π-π堆积作用形成二维超分子层状结构。化合物9的晶体结构中,相邻的[Co2(L)2(phen)2]单元通过π-π作用形成一维双链超分子结构。化合物10和11的一维链借助于π-π作用形成二维超分子层。π-π堆积和氢键作用将化合物12中的[Cd2(L)2(phen)2]单元进一步连接形成三维超分子构型。化合物13的层状结构具有典型的(4,4)拓扑结构,这些层状结构通过π-π堆积形成三维超分子结构。化合物14的二聚体[Pb2(L)2(phen)2]单元通过π-π堆积作用形成二维超分子结构。此外本论文还对化合物的热重和发光性质进行了研究。
【Abstract】 Fourteen novel coordination compounds based on (4-carboxyphenyl)(4-(2-carboxyphenyl)benzyl) ether (H2L) and N-donor ligands have been hydrothermallysynthesized and structurally determined by single-crystal X-ray diffraction analyses, namely,[Zn3(L)3(biim-4)2]·H2O (1),[Cd(L)(H2O)(biim-4)0.5](2),[Zn(L)(BIE)](3),[Co(L)(BIE)](4),[Cd(L)(BIE)](5),[Ni(L)(BIE)](6),[Ni(L)(phen)]·H2O (7),[Co(L)(phen)]·H2O (8),[Co(HL)2(phen)2]·3H2O (9),[Cd(L)(H2O)(phen)](10),[Co(L)(H2O)(phen)](11),[Cd(L)(phen)2](12),[Pb(L)](13), and [Pb(L)(phen)]·H2O (14), where biim-4=1,1’-(1,4-butanediyl)bis(imidazole), BIE=2,2’-bis(1-imidazolyl)ether, and phen=1,10-phenanthroline. Compound1displays an unusual3D binodal (4,5)-connected net withPoint Symbol of (43·62·8)(45·5·64). Compound2exhibits1D loop-like chain structures, whichare further extended into a3D supramolecular architecture through π-π interactions.Compounds3-6are isomorphous, and feature similar2D layer structures. Compounds7and8are isomorphous, and show the same0D structures, which are further extended by π-πinteractions into2D supramolecular layers. Compound9displays a discrete [Co2(L)2(phen)2]dimer. Neighboring dimers are further linked by π-π interactions to form a1D double chain.Compounds10and11exhibit the similar1D double chain structures. The chains are furtherlinked via π-π interactions to generate2D supramolecular layers. Compound12shows adiscrete [Cd2(L)2(phen)2] dimer. The π-π stacking and hydrogen-bonding interactions furtherextend the dimers into a3D supramolecular architecture. Compound13displays a typical(4,4) network structure. Neighboring networks are further linked by the π-π interactions,leading to an unusual3D supramolecular architecture. Compound14exhibits a discrete[Pb2(L)2(phen)2] dimer. Neighboring dimers are further linked by the π-π interactions to forma2D supramolecular layer. The thermal stabilities and luminescent properties of thecomplexes have also been investigated in detail.
【Key words】 Coordination compound; Supramolecule; N-donor ligands; π-π interaction; Hydrogen bonds;