基于原位脱羧3-硝基邻苯二甲酸构筑的金属配合物的合成、晶体结构及物理性质

Metal Complexes Based on 3-Nitrophthalic Acid Involving in Situ Decarboxylaton:Syntheses,Crystal Structures and Physical Properties

利用水热反应以3-硝基邻苯二甲酸(3-NPAH2)和菲咯啉(phen)或1,2,4-三氮唑(Htrz)分别与ZnSO4·7H2O和Pb(NO3)2反应,成功组装了2个配合物:[Zn(3-NBA)(trz)]n(1)、[Pb(3-NBA)(phen)2]NO3(2)。在反应过程中3-硝基邻苯二甲酸发生了原位脱羧反应而产生3-硝基苯甲酸(3-HNBA),理论计算也证实了实验结果。利用红外光谱、粉末XRD、元素分析和热重分析等方法对2个配合物进行了表征。单晶结构解析结果显示:配合物1具有二维层状结构,层与层之间存在N-O…π弱相互作用。配合物2具有零维单核结构,这些单核单元通过π…π弱相互作用进一步形成了三维超分子结构。此外,还研究了2个配合物室温条件下的固体荧光性质。

Two metal complexes,[Zn(3-NBA)(trz)]n(1)and[Pb(3-NBA)(phen)2]NO3(2),have been constructed through hydrothermal reaction using 3-nitrophthalic acid(3-NPAH2),phen(1,10-phenanthroline)or 1,2,4-triazole(Htrz),and ZnSO4·7H2O or Pb(NO3)2.During the reaction,the 3-HNBA resulted from the in situ decarboxylation of 3-nitrophthalic acid,and the experimental results have been confirmed by the theoretical calculation.Complexes 1~2 have been characterized by IR spectra,PXRD,elemental analyses and thermogravimetric analyses.Single-crystal X-ray diffraction analyses reveal that complex 1 exhibits a two-dimensional(2D)layered structure,which packs through weak N-O…πinteractions.Complex 2 has a monomeric structure,which is assembled to a three-dimensional(3D)supramolecular structure through weakπ…πinteractions.Furthermore,the solid-state fluorescence of complexes 1~2 was recorded at room temperature.CCDC:1915797,1;1915798,2.