基于[LnMo_(12)]二十面体的三维稀土钼酸盐骨架的合成、结构及荧光性能(英文)  

Synthesis,crystal structure,and luminescence properties of three-dimensional rare earth molybdate framework based on[LnMo12]icosahedron

作　　者：黄敏 卓著[1,2,3] 陈婷 路自修[2,3] 王维[1,2,3,4] 黄有桂 HUANG Min;ZHUO Zhu;CHEN Ting;LU Zi-Xiu;WANG Wei;HUANG You-Gui(College of Chemistry and Materials Science,Fujian Normal University,Fuzhou 350002,China;CAS Key Laboratory of Design and Assembly of Functional Nanostructures,Fujian Provincial Key Laboratory of Nanomaterials,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China;Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials,Xiamen Institute of Rare Earth Materials,Haixi Institutes,Chinese Academy of Sciences,Xiamen,Fujian 361021,China;Fujian College,University of Chinese Academy of Sciences,Fuzhou 350002,China)

机构地区：[1]福建师范大学化学与材料学院,福州350002 [2]中国科学院福建物质结构研究所,中国科学院功能纳米结构设计与组装重点实验室,福建省纳米材料重点实验室,福州350002 [3]中国科学院海西研究院厦门稀土材料研究所,稀土光电功能材料厦门重点实验室,厦门361021 [4]中国科学院大学福建学院,福州350002

出　　处：《无机化学学报》2023年第11期2209-2218,共10页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21871262,21901242);福建省自然科学基金(No.2020J05080);厦门自然科学基金(No.3502Z20206080);中国科学院重点研究计划(No.ZDRW-CN-2021-3-3)和中国科学院青年创新促进会(No.2021302)资助。

摘　　要：通过缓慢蒸发溶剂法合成了2例新的三维稀土钼酸盐:[Ln(H_(2)O)_(3)]_(3)[LnMo_(12)O_(42)]·xH_(2)O,其中Ln=Eu(1)、Tb(2),x=7(1),10.17(2)。这2种稀土钼酸盐中都含有新颖的二十面体[LnMo_(12)O_(42)]构建单元,该单元通过与{LnO_(9)}多面体进一步连接形成三维网络。光致发光测试表明,化合物1和2显示出明显不同的发射特征,这与Eu^(3+)和Tb^(3+)离子的不同能级跃迁密切相关。化合物1表现出较强的红色发射(CIE色度坐标为(0.66,0.33))、高发光强度、较大的荧光量子产率(约60%),对应于从5D0到^(7)F_(J)(J=4、3、2、1、0)的跃迁;化合物2表现出浅绿色发射(CIE色度坐标为(0.34,0.60)),对应从^(5)D_(4)到^(7)F_(J)(J=6、5、4、3)的能级跃迁,其发光强度较弱和荧光量子产率较低(约20%)。有趣的是,一定量的Tb^(3+)引入和大量溶剂分子的存在导致化合物2发生部分荧光猝灭,但对化合物1的荧光几乎没有影响。Two new 3D rare-earth molybdate frameworks,[Ln(H_(2)O)_(3)]_(3)[LnMo_(12)O_(42)]·xH_(2)O,where Ln=Eu(1),Tb(2);x=7(1),10.17(2),have been synthesized by slow evaporation.Both of these rare earth molybdate frameworks have a new rare-earth-centered icosahedron[LnMo_(12)O_(42)]building unit,which is further connected to adjacent ones by{LnO_(9)}polyhedra to form a 3D network.Photoluminescence tests reveal that 1 and 2 exhibited different emission properties,which are caused by the f-orbital energy levels of Eu^(3+)and Tb^(3+).1 exhibited bright red emissions(CIE chromaticity coordinates:(0.66,0.33))corresponding to the transition from 5D0 to^(7)F_(J)(J=4,3,2,1,0),with high luminescent emission intensity and high quantum yield(about 60%).2 exhibited light green emissions(CIE chromaticity coordinates:(0.34,0.60))corresponding to the transition from^(5)D_(4)to^(7)F_(J)(J=6,5,4,3),with lower luminescent emission intensity and quantum yield(about 20%).Interestingly,the introduction of Tb and the presence of a large number of solvent molecules in compound 2,both lead to partial fluorescence quenching but have little effect on the fluorescence properties of 1.CCDC:2254280,1;2254281,2.

关 键 词：稀土钼酸盐 晶体结构 光致发光 荧光淬灭 配位化学 荧光粉 

分 类 号：O614.338[理学—无机化学] O614.341[理学—化学]