摘要
合成了3个香豆素Schiff碱单核Zn^(2+)、Co^(2+)和双核Ni^(2+)的配合物,[Zn(L^(1))_(2)](1)(HL^(1)=6‑((4‑二乙胺基‑2‑羟基‑亚苄基)‑氨基)‑苯并吡喃‑2‑酮),[Co(L^(2))_(2)](2)(HL^(2)=6‑((4‑甲氧基‑2‑羟基-亚苄基)‑氨基)‑苯并吡喃‑2‑酮),[Ni_(2)(L^(3))_(2)(CH_(3)OH)_(4))](3)(H_(2)L^(3)=4‑羟基‑3‑((4‑甲氧基‑2‑羟基-亚苄基)‑氨基)‑苯并吡喃‑2‑酮)。利用元素分析、红外光谱、紫外可见光谱、荧光光谱及X射线单晶衍射分析等手段对其进行了表征。X射线单晶衍射分析结果表明:配合物1和配合物2均为单核结构,由1个金属离子和2个配体单元组成;配合物3具有双核结构,由2个金属离子、2个配体单元及4个配位的甲醇分子组成。配合物1、2和3分别是单斜晶系、三斜晶系和三斜晶系,所属的空间群分别为C2/c、P1和P21/n;中心金属Zn^(2+)和Co^(2+)离子的空间构型为四配位的四面体,Ni^(2+)离子的空间构型为六配位的扭曲的八面体。此外,通过对配体HL^(1)和HL^(2)的紫外可见光谱性质研究发现,在DMF/H_(2)O(4∶1,V/V)溶液中,自由配体HL^(1)和HL^(2)分别可以选择性识别Hg^(2+)和Zn^(2+),通过计算得到其检测限分别为7.45和6.10μmol·L^(-1)。荧光性质研究发现在DMF/H_(2)O(4∶1,V/V)溶液中自由配体HL^(2)可以检测Zn^(2+),检测限为2.91μmol·L^(-1)。
Mononuclear Zn^(2+),Co^(2+)complexes and binuclear Ni^(2+)complex based on coumarin Schiff base ligands,[Zn(L^(1))_(2)](1)(HL^(1)=6‑((4‑diethylamino‑2‑hydroxy‑benzylidene)‑amino)‑benzopyran‑2‑one),[Co(L^(2))_(2)](2)(HL^(2)=6‑((4‑methoxy‑2‑hydroxy‑benzylidene)‑amino)‑benzopyran‑2‑one)and[Ni_(2)(L^(3))_(2)(CH_(3)OH)_(4)](3)(H_(2)L^(3)=4‑hydroxy‑3‑((4‑methoxy‑2‑hydroxy‑benzylidene)‑amino)‑benzopyran‑2‑one),were synthesized and characterized by elemental analysis,IR,UV‑Vis,fluorescence spectra and X‑ray single crystal diffraction analysis.The crystal structure analysis represents that the complexes 1 and 2 possess mononuclear structure composed of one metal ion(Zn^(2+)or Co^(2+))and two ligand units((L^(1))-or(L2)‒).Whereas complex 3 had binuclear structure,containing two Ni^(2+)ions,two ligand units(L^(3))_(2)-and four coordination methanol molecules.The crystals of complexes 1,2 and 3 are solved as monoclinic space group C2/c,triclinic space group P1 and triclinic space group P21/n,respectively.The spatial configurations of the central metal Zn^(2+)and Co^(2+)ions are four‑coordinated tetrahedrons,and the Ni^(2+)ion is six‑coordinated twisted octahedrons.In addition,UV‑Vis studies demonstrate that the free ligands HL^(1) in DMF/H_(2)O(4∶1,V/V)solution and HL^(2) in DMSO/H_(2)O(4∶1,V/V)solution could selectively recognize Hg^(2+)and Zn^(2+),respectively.The detection limits were calculated to be 7.45 and 6.10μmol·L^(-1),respectively.Fluorescence studies indicate that HL^(2) exhibits ability of selective recognition Zn^(2+)against other common cationic including Ag+,Ba2+,Ca2+,Cd2+,Cr3+,Cu2+,Fe3+,Mg2+,Mn2+and Hg^(2+)in DMSO/H_(2)O(4∶1,V/V),and the detection limit was calculated to be 2.91μmol·L^(-1).CCDC:2034542,1;2034547,2;2034548,3.
作者
郭耿
李娟
武娅
丁文敏
张淑珍
孙银霞
GUO Geng;LI Juan;WU Ya;DING Wen‑Min;ZHANG Shu‑Zhen;SUN Yin‑Xia(School of Chemical and Biological Engineering,Lanzhou Jiaotong University,Lanzhou 730070,China)
出处
《无机化学学报》
SCIE
CAS
CSCD
北大核心
2021年第6期1113-1124,共12页
Chinese Journal of Inorganic Chemistry
