基于2-(3-吡啶基)-1H-吡唑-苯羧酸的三种镉(Ⅱ)配合物晶体结构、荧光表征和Hirshfeld表面分析  

Crystal structures,luminescent properties and Hirshfeld surface analyses of three cadmiumcomplexes based on 2⁃(3⁃(pyridin⁃2⁃yl)⁃1H⁃pyrazol⁃1⁃yl)benzoate

作　　者：张力杨 杨冬冬 李宁 杨元宇 马琦[1] ZHANG Liyang;YANG Dongdong;LI Ning;YANG Yuanyu;MA Qi(School of Chemistry and Environmental Engineering,Shanxi Datong University,Datong,Shanxi 037009,China)

机构地区：[1]山西大同大学化学与化工学院,应用化学研究所,大同037009

出　　处：《无机化学学报》2024年第10期1943-1952,共10页Chinese Journal of Inorganic Chemistry

基　　金：山西省高等学校科技创新计划项目(No.2023L267)资助。

摘　　要：基于2⁃(3⁃吡啶基)⁃1H⁃吡唑-苯羧酸(Hppb)配体,成功合成3种溴离子参与配位的不同Cd(Ⅱ)配合物[Cd(Hppb)_(2)Br_(2)](1)、[Cd_(2)(ppb)_(2)Br_(2)](2)和[Cd(Hppb)Br_(2)]n(3),并确定了其结构特征。在3种配合物中,Cd(Ⅱ)离子、配体、溴离子的比例分别为1∶2∶2、1∶1∶1、1∶1∶2,最终得到单核(0D)、双核(0D)、一维骨架的不同结构。配合物1中的Cd(Ⅱ)配位环境为轻微扭曲的八面体几何结构,而配合物2和3的中心离子则显示出扭曲的四方锥几何结构。3个配合物的ppb-或Hppb配体的连接模式存在明显差异。在配合物1中,2个Hppb配体为μ_(1)⁃κN,N'配位模式。而在配合物2中,2个ppb-配体为μ_(2)⁃κN,N'∶κO配位模式,并且作为2个μ1,1桥连接2个Cd(Ⅱ)离子形成双核结构单元,2个Cd离子之间的距离为0.4091(4)nm。在3中,中性Hppb配体为μ_(2)⁃κN,N'∶κO配位模式,并通过μ1,6桥连接Cd(Ⅱ)离子,沿b轴形成一维无限延长的链。利用Hirshfeld表面分析和二维指纹图对这3种配合物进行了研究。此外,配合物1~3的光致发光特性表明,配位阴离子Br-对Cd(Ⅱ)配合物的荧光发射有很大影响。We have successfully synthesized three cadmiumcomplexes[Cd(Hppb)2Br_(2)](1),[Cd_(2)(ppb)_(2)Br_(2)](2)and[Cd(Hppb)Br_(2)]n(3)in which the bromide ions are involved based on an asymmetric ligand 2⁃(3⁃(pyridin⁃2⁃yl)⁃1H⁃pyrazol⁃1⁃yl)benzoate(Hppb).Employment of different synthetic conditions has resulted in different architectures.In the three complexes,the ratios of Cdions,ligands,and bromide ions were 1∶2∶2,1∶1∶1,and 1∶1∶2,respec⁃tively,resulting in different structures of mononuclear(0D),binuclear(0D),and 1D framework.The Cdcoordinat⁃ed environments in 1 are slightly distorted octahedral geometries,but central ions in 2 and 3 display distorted square pyramidal geometries.There are obvious differences in the ligation modes of the ppb-or Hppb ligands for both complexes.In 1,two Hppb ligands displayμ_(1)⁃κN,N'coordination modes.In 2,two ppb-ligands displayμ_(2)⁃κN,N'∶κO coordination modes.Two ppb-ligands act as twoμ_(1),1⁃bridges linking the binuclear Cdcations with a distance of 0.4091(4)nm.In 3,the neutral Hppb ligands exhibit aμ_(2)⁃κN,N'∶κO coordination mode,and connecting Cd(Ⅱ)ions byμ1,6⁃bridges and forming an infinite 1D chain along the b⁃axis.The complexes were both studied using Hirshfeld surface analyses and 2D fingerprint plots.Moreover,the photoluminescent properties of 1⁃3 indicate that the coordination anions make a great contribution to the fluorescent emission of Cd(Ⅱ)polymers.CCDC:2302311,1;2302312,2;2302313,3.

关 键 词：2⁃(3⁃吡啶基)⁃1H⁃吡唑-苯羧酸 Cd(Ⅱ)配合物 发光特性 

分 类 号：O614.242[理学—无机化学]