基于5-磺基水杨酸的单、双核铜(Ⅱ)三元混配配合物的合成及晶体结构

以5-磺基水杨酸和咪唑衍生物为配体合成了单核、双核结构的三元混配Cu(Ⅱ)配合物:Cu(H₂biim)(Hssal)(H₂O)₂]·H₂O(1)和{Cu(MeHbiim)(Hssal)(H₂O)]·0.5H₂O}₂(2)(H₃ssal=5-磺基水杨酸,H₂biim=2,2’-联咪唑,MeHbiim=N-甲基-2,2’-联咪唑),并利用元素分析、红外光谱、紫外-可见光谱、X-射线单晶衍射及热重分析等技术手段对其结构进行了表征。单晶结构解析表明配合物1属于单斜晶系,P2₁／C 空间群,Cu(Ⅱ)离子与1个5-磺基水杨酸根、2个水分子以及1个联咪唑分子形成五配位四角锥构型的单核配合物结构。配合物2属于正交晶系,P2(1)2(1)2(1)空间群,双核Cu(II)离子分别处于五配位四角锥和四配位平面四边形的几何构型的配位环境中,与配合物1不同,5-磺基水杨酸采取μ₂双-单齿配位模式。荧光光谱分析表明配合物2具有较强的荧光性。

Synthesis and Crystal Structure of Mono-, Binuclear Copper(Ⅱ) Ternary Complexes Based on 5-Sulfosalicylic Acid

Mono- and binuclear structure of ternary complexes of Cu(Ⅱ):Cu(H₂biim)(Hssal) (H₂O)₂]·H₂O(1) and {Cu(MeHbiim)(Hssal)(H₂O)]·0.5H₂O}₂ (2) (H₃ssal=5-sulfonylsalicylic acid, H₂biim=2,2′-diimidazole, MeHbiim=N-methyl-2,2′-diimidazole) were synthesized using 5-sulfosalicylic acid and imidazole derivatives as the ligands. The structures were characterized by elemental analysis, IR, UV-Vis, single crystal X-ray diffraction and TG analysis. X-ray crystallographic studies show that complex 1 belongs to monoclinic, P2₁/C space group. Each Cu (Ⅱ) ion is coordinated with one 5-sulfosalicylic acid anion, two water molecules and one biimidazole molecule to form five-coordinated mononuclear structural unit of distorted square pyramidal configuration. Binuclear Cu(II) complex 2 exhibits orthorhombic, P2(1)2(1)2(1) space group. One Cu(II) ion of binuclear structural unit is five-coordinated with geometry of square pyramid same as complex 1 and another Cu(II) ion is four-coordinated with geometry of quadrilateral plane. Compared to complex 1, 5-sulfonyl salicylic acid anion acted as a μ₂ bis-monodentate bridging ligand in complex 2. The fluorescence spectrum analysis shows that the complex 2 has good fluorescence property.