Zheng Xiang-Jun, Ablet Ayjamal, Ng Christie, Wong Wing-Tak
Beijing Key Laboratory of Energy Conversion and Storage Materials, College of Chemistry, Beijing Normal University , Beijing, 100875, People's Republic of China.
Inorg Chem. 2014 Jul 7;53(13):6788-93. doi: 10.1021/ic500592k. Epub 2014 Jun 13.
Four novel heterometallic RE-Na-organic frameworks, [(RE)Na3(PZTC)2(H2O)4]·2H2O (RE = Yb (1), Ho (2), Er (3), Y (4); PZTC = pyrazine-2,3,5-tricarboxylate), were synthesized via solvothermal reactions and characterized by IR, elemental analysis, and single-crystal X-ray diffraction. The results show that the four complexes are isostructural. In the frameworks, the trinuclear Na cluster and RE ion acting as nodes are bridged by the multifunctional PZTC ligand to give a 3-D framework. Codoping in the frameworks was realized due to their isostructural characteristics. The codoped complexes were calcinated at 800 °C to give rise to the corresponding oxides. Investigation of their photophysical properties shows that the upconversion luminescence (UCL) of the Ho system is green while that of the Er system is red upon excitation at 980 nm. With regard to the luminescence color and intensity, the Er system is preferable to the Ho system for application in bioimaging. Both the red and the green UCL of the Ho(3+) and Er(3+) systems involve a two-photon process. In addition, the UCL mechanism is given. The UCL comparison of Na-doped oxides with non-Na-doped oxides indicates that doping Na can greatly enhance the UCL of the Er system.
通过溶剂热反应合成了四种新型异金属稀土-钠有机框架化合物[(RE)Na3(PZTC)2(H2O)4]·2H2O(RE = Yb (1)、Ho (2)、Er (3)、Y (4);PZTC = 吡嗪-2,3,5-三羧酸),并通过红外光谱、元素分析和单晶X射线衍射对其进行了表征。结果表明,这四种配合物具有同构结构。在框架结构中,作为节点的三核钠簇和稀土离子由多功能的PZTC配体桥连,形成三维框架。由于它们的同构特性,实现了框架内的共掺杂。将共掺杂的配合物在800℃煅烧,得到相应的氧化物。对其光物理性质的研究表明,在980nm激发下,Ho体系的上转换发光(UCL)为绿色,而Er体系的为红色。就发光颜色和强度而言,Er体系在生物成像应用中优于Ho体系。Ho(3+)和Er(3+)体系的红色和绿色UCL均涉及双光子过程。此外,还给出了UCL机制。Na掺杂氧化物与非Na掺杂氧化物的UCL比较表明,掺杂Na可以大大增强Er体系的UCL。