钴配位聚合物的晶体、电化学和对EY^(2-)的荧光淬灭性能

Synthesis,electrochemistry and fluorescence quenching EY^(2-) performance of cobalt coordination polymer

以单核钴配位聚合物[Co(dmgH)(dmgH_2)Cl_2](1)为合成中间体,以4,4′-联吡啶(4,4′-bipy)为桥联配体,并加少量的乙二胺调节pH,进行水热合成得到一个新的二维网状配聚物[Co_(1.5)(4,4’-bipy)·(dmgH_2)_(1.5)·(H_2O)]_n·(en)_n·(13H_2O)_n(2),X射线单晶衍射分析结果表明,该配聚物属正交晶系,Pbcn空间群(60号空间群).晶胞参数为:a=2.546 30(8)nm,b=1.591 56(6)nm,c=1.636 22(5)nm;α=90.00°,β=90.00°,γ=90.00°,V=6.630 9(4)nm_3,Z=4,F(000)=2 812.00.晶体结构分析表明,配聚物Co(Ⅲ)中心离子为六配位扭曲的八面体构型,通过4,4-联吡啶的N原子桥联成二维网状结构,二维网状结构通过苯环之间弱的π-π作用力堆积成三维固态结构.循环伏安和荧光淬灭实验表明,该化合物具有较低的氧化还原电位,并对曙红Y(EY^(2-))具有很强的荧光淬灭作用,可作为潜在的光化学还原催化剂用于光催化分解水制氢.

A new two-dimensional network cobalt coordination polymer {[Co 1.5 （4,4＇-bipy）·（dmgH 2） 1.5 ·（H 2O）] n ·（en） n ·（13H 2O） n }（ 2 ） was synthesized by hydrothermal synthesis method using a mononuclear cobalt complex [Co （dmgH） （dmgH 2） Cl 2] （ 1 ） as synthesis intermediate and 4,4- bipyridine （4,4＇-bipy） as bridging ligand, a small amount of ethylenediamine（en） was used to adjust the pH. The results of single crystal X-ray diffraction analysis show that the polymer crystalizes in orthorhombic, space group P bcn. Cell Parameters are as follows： a =2.546 30 （8） nm, b =1.591 56 （6） nm, c =1.636 22 （5）nm; α =90.00°, β =90.00°, γ =90.00°, V =6.630 9（4） nm 3, Z =4, F （000）=2 812.00. The crystal structure analysis shows that the Co（Ⅲ） cation is a six-coordinated distorted octahedron with a 4,4’-bipyridyl N atom bridged into a two-dimensional network structure . The two-dimensional network structure stacked into three-dimensional solid structure by weak π-π force. Cyclic voltammetry and fluorescence quenching experiments show that the title coordination polymer has a low redox potential and has a strong fluorescence quenching effect on eosin Y. It can be used as a potential photochemical reduction catalyst for the photocatalytic decomposition of water to obtain hydrogen.