系列Ag-Ln配位聚合物的合成、结构及发光性能  

Syntheses, Crystal Structures and Luminescent Properties of Ag-Ln Coordination Polymers

作　　者：王岩[1] 陈飞霏 胡晓双 赵然[1] 迟玉贤[1] 金晶[1] WANG Yan;CHEN Fei-Fei;HU Xiao-Shuang;ZHAO Ran;CHI Yu-Xian;JIN Jing(School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, Liaoning 116029, China)

机构地区：[1]辽宁师范大学化学化工学院,大连116029

出　　处：《无机化学学报》2019年第2期225-235,共11页Chinese Journal of Inorganic Chemistry

基　　金：辽宁省教育厅青年基金(No.201783635);辽宁省自然科学基金(No.20170540576)资助项目

摘　　要：采用水热合成法,以吡嗪-2-羧酸(2-Hpzc)、3,5-吡啶二羧酸(3,5-H_2PDA)和草酸(H_2ox)为配体,合成9种Ag-Ln配位聚合物:{[LnAg(2-pzc)_2(ox)]·H_2O}_n(Ln=Pr(1),Nd(2),Sm(3),Eu(4)),[LnAg(3,5-PDA)(ox)(H_2O)]_n(Ln=Pr(5),Nd(6)),[LnAg(3,5-PDA)(3,5-HPDA)(ox)_(0.5)(H_2O)_2]_n(Ln=Sm(7),Dy(8),Ho(9))。配位聚合物1～4是同构的,由2-pzc^-和ox^(2-)连接,而配位聚合物5～9是以3,5-PDA^(2-)和ox^(2-)为桥联配体,均呈现3D网状结构。光物理性能研究表明配位聚合物均表现出Ln(Ⅲ)的特征发射,这可归因于Ag-配体部分(d-block)的敏化作用。另外,在晶体场和Ag(1)离子4d轨道的共同作用下,Ln(Ⅲ)离子的4f轨道被调谐,使部分能级发生明显的位移,表现为相应NIR发射带的位移,在其UV-Vis-NIR吸收光谱中可以得到佐证。Using pyrazine-2-carboxylic acid (2-Hpzc), 3,5-pyridinedicarboxylic acid (3,5-H2PDA) and oxalic acid (H2ox) as ligands, nine Ag-Ln coordination polymers are synthesized by hydrothermal methods:{[LnAg(2-pzc)2(ox)]·H2O}n (Ln=Pr (1), Nd (2), Sm (3), Eu (4)),[LnAg(3,5-PDA)(ox)(H2O)]n (Ln=Pr (5), Nd (6)),[LnAg(3,5-PDA)(3,5- HPDA)(ox)0.5(H2O)2]n (Ln=Sm (7), Dy (8), Ho (9)). All of them possess the 3D network structure, i.e., coordination polymers 1~4 are isomorphic and connected by 2-pzc- and ox2-, while coordination polymers 5~9 use 3,5-PDA2- and ox2- as bridging ligands. Photophysical properties of these coordination polymers are studied, and they show characteristic emissions of corresponding Ln(Ⅲ)ions which should be attributed to the sensitization of the Agligand section (d-block). In addition, under the co-action of crystal field and 4d orbits of Ag(Ⅰ)ion, the 4f orbits of Ln(Ⅲ)ions are tuned and cause obvious shift of partial energy levels, which present shifts of the corresponding NIR emission bands and can be corroborated in their UV-Vis-NIR absorption spectra. CCDC: 1817276, 1;1817247, 2;1817248, 3;1817249, 4;1817251, 5;1817255, 6;1817269, 7;1817280, 8;1817285, 9.

关 键 词：Ag-Ln配位聚合物 晶体结构 敏化 发光性能 

分 类 号：O614.334[理学—无机化学] O614.335[理学—化学]