两个Co/Ni含氮配体配合物的合成、结构及荧光性质

Syntheses, Structures and Fluorescent Properties of Two Co/Ni Complexes with Nitrogen⁃Donor Ligands

陈贤 柳畅 王莹 关磊 尹鹏鹏 熊学佳 金红哲

Xian Chen Chang Liu Ying Wang Lei Guan Pengpeng Yin Xuejia Xiong Hongzhe Jin

辽宁石油化工大学 石油化工学院，辽宁 抚顺 113001

School of Petrochemical Engineering，Liaoning Petrochemical University，Fushun Liaoning 113001，China

以1,4?二羟基苯?2?磺酸钠（NaH2L）、4,4'?联吡啶（bipy）、Co(NO3)2·6H2O和NiSO4·6H2O为原料，采用加热回流的方法，得到两个结构相似的单核含氮配体配合物M(bipy)(H2O)4·(2H2L)·4H2O（M=Co（1），Ni（2）），其结构和组成采用单晶X?射线衍射、元素分析以及热重分析进行表征。结果表明，Co2+和Ni2+是六配位的，呈八面体配位构型，均与一个bipy分子和四个水分子配位；H2L-没有与金属离子配位，起到平衡电荷作用；配合物中，H2L-、自由的水分子以及[M(bipy)(H2O)4]2+形成氢键，这些氢键将其连接构成了网状结构，增加了配合物的稳定性。荧光研究结果表明，配合物1和配合物2的最大荧光发射峰分别在380 nm和390 nm，均是NaH2L的特征荧光发射峰。金属和配体间的电荷转移促使其荧光发射峰红移。

Using sodium 1,4?dihydroxybenzene?2?sulfonate sodium (NaH2L), 4,4'?bipyridine (bipy), Co(NO3)2·6H2O and NiSO4·6H2O as raw materials, two mononuclear complexes containing nitrogen?donor ligands with similar structures, M(bipy)(H2O)4·(2H2L)·4H2O（M=Co（1）， Ni（2））, were synthesized by heating reflux method. The molecular structurse and composition were determined by single crystal X?ray diffraction, elemental analyses and thermogravimetric analyses. Co2+ and Ni2+ are six?coordinated, showing octahedral configuration, which are binded with one bipy molecule and four water molecules. H2L- anion does not coordinate with metal ions, balancing charges. In the complexes, H2L- anions, free water molecules and [M(bipy)(H2O)4]2+ cations can generate hydrogen bonds, which can form a network structure and increase the stability of the complexes. The fluorescence studies indicate that the maximum emission peaks of complexes 1 and 2 were 380 nm and 390 nm, respectively, which are characteristic fluorescence emission peaks of NaH2L. The red shifts of the fluorescence emission peaks were due to the charge transfers between metal and ligand.

辽宁省教育厅科学研究项目(L2019010)

10.3969/j.issn.1672-6952.2021.06.003