高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (7): 1125-1133.doi: 10.7503/cjcu20160958

• 研究论文: 无机化学 • 上一篇    下一篇

1,3-二(4-吡啶基)-丙烷与邻苯二甲酸构筑的过渡金属配合物的合成、结构和荧光性质

王秋爽, 郑晓丽, 屈相龙, 李睿, 李夏()   

  1. 首都师范大学化学系, 北京 100048
  • 收稿日期:2016-12-29 出版日期:2017-07-10 发布日期:2017-05-02
  • 作者简介:联系人简介: 李 夏, 女, 博士, 教授, 博士生导师, 主要从事无机配位化学研究. E-mail: xiali@cnu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 21471104)和首都师范大学科技创新服务能力建设-科研水平提高定额-交叉科研项目资助

Synthesis, Structure and Luminescence Property of Transition Metal Complexes with 1,3-Di(4-pyridyl)-propane and 1,2-Benzenedicarboxylic Acid

WANG Qiushuang, ZHENG Xiaoli, QU Xianglong, LI Rui, LI Xia*()   

  1. Department of Chemistry, Capital Normal University, Beijing 100048, China
  • Received:2016-12-29 Online:2017-07-10 Published:2017-05-02
  • Contact: LI Xia E-mail:xiali@cnu.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No;21471104) and the Cross Scientific Research Projects, Capital Normal University, China

摘要:

以1,3-二(4-吡啶基)-丙烷(bpp)和邻苯二甲酸(1,2-H2bdc)为配体, 通过水热法合成了过渡金属配合物M2(1,2-bdc)2(bpp)2·2H2O[M=Co(1), Ni(2)]和Cd(1,2-bdc)(bpp)·H2O(3). 配合物1和2属单斜晶系P21空间群, 具有相似的三维骨架结构. 配合物中存在2种配位环境相似的金属中心, 每个金属中心采取六配位的畸变八面体构型, 与来自2个1,2-bdc配体的3个氧原子和2个bpp配体的2个氮原子以及1个水分子配位. 1,2-bdc配体采取单齿/双齿螯合的配位模式将金属离子连接成M1-(1,2-bdc)-M2右手螺旋链. bpp配体采取Trans-Gauche(TG)构型, 连接相邻的金属离子形成M1-(bpp)-M1链和M2-(bpp)-M2链. 这3种链交织在一起构筑成具有{65. 8}拓扑的三维结构. 配合物3属单斜晶系P21/c空间群, 具有单节点的双层二维结构. Cd(Ⅱ)离子采取七配位的畸变五角双锥体构型, 与来自2个1,2-bdc配体的4个氧原子, 2个bpp配体的2个氮原子和1个水分子配位. 1,2-bdc配体采取双齿螯合/双齿螯合的配位模式将Cd(Ⅱ)离子连接成Cd-(1,2-bdc)-Cd链. bpp配体采取TG构型, 连接相邻的Cd(Ⅱ)离子, 形成Cd-(bpp)-Cd链. 这2种链通过共享Cd(Ⅱ)离子交错排列构筑成二维结构. 配合物3显示出强的荧光, 最大发射位于408 nm处, 对应于配体的π*跃迁. 不同有机小分子对配合物3的荧光强度有不同程度的影响, 苯胺对其有显著的猝灭作用, 基于荧光猝灭机理, 配合物3可用于选择性检测苯胺分子.

关键词: 过渡金属配合物, 1, 3-二(4-吡啶基)-丙烷, 邻苯二甲酸, 晶体结构, 荧光

Abstract:

Taking 1,3-di(4-pyridyl)-propane(bpp) and 1,2-benzenedicarboxylic acid(1,2-H2bdc) as ligands, three new transition metal complexes, M2(1,2-bdc)2(bpp)2·2H2O[M(Ⅱ)=Co(1), Ni(2)] and Cd(1,2-bdc)(bpp)·H2O(3), were obtained. Complexes 1 and 2 crystallize in monoclinic crystal system with space group P21 and show 3D structures with {65·8} topology. There are two M(Ⅱ) centers with the similar coordination environments in complexes 1 and 2. Each M(Ⅱ) center is six-coordinated to three oxygen atoms from two 1,2-bdc ligands, two nitrogen atoms from bpp ligands and one water molecule in a distorted octahedral arrangement. The 1,2-bdc ligand adopts monodentate bridging/bidentate chelating mode to link two metal centers to form M1-(bpp)-M1 right-handed-helical chain. The bpp ligand adopts Trans-Gauche(TG) conformation and connects adjacent M(Ⅱ) centers to form M1-(bpp)-M1 and M2-(bpp)-M2 chains. These three kinds of chains are woven together to form a 3D framework. Complex 3 crystallizes in monoclinic crystal system with space group P21/c and shows a 2D structure. The Cd(Ⅱ) is in distorted pentagonal bipyramidal polyhedron with four oxygen atoms of two 1,2-bdc ligands, two nitrogen atoms of bpp ligand and one water molecule. The 1,2-bdc ligand adopts bi(bidentate chelating) mode to link Cd(Ⅱ) centers to form Cd-(1,2-bdc)-Cd chain. The bpp ligand adopts TG conformation and connects Cd(Ⅱ) centers to form Cd-(bpp)-Cd chain. The two kinds of chains with shared Cd(Ⅱ) are alternately arranged to form a 2D structure. Complex 3 shows strong ligand-based fluorescence with maximum emission at 408 nm, which is attributed to π* transition of the ligands. Different organic small molecules have different effects on the fluorescence intensity of complex 3, and aniline has a significant quenching effect, thus complex 3 can be used for the selective detection of aniline through fluorescence quenching mechanism.

Key words: Transition metal complex, 1, 3-Di(4-pyridyl)-propane, 1, 2-Benzenedicarboxylic acid, Crystal structure, Fluorescence