Excimer Formation in a Terbium Metal-Organic Framework Assists Luminescence Thermometry

被引:65
|
作者
Ananias, Duarte [1 ,2 ]
Firmino, Ana D. G. [1 ]
Mendes, Ricardo F. [1 ]
Almeida Paz, Filipe A. [1 ]
Nolasco, Mariela [1 ]
Carlos, Luis D. [2 ]
Rocha, Joao [1 ]
机构
[1] Univ Aveiro, CICECO Aveiro Inst Mat, Dept Chem, P-3810193 Aveiro, Portugal
[2] Univ Aveiro, CICECO Aveiro Inst Mat, Dept Phys, P-3810193 Aveiro, Portugal
关键词
COORDINATION POLYMERS; LANTHANIDES;
D O I
10.1021/acs.chemmater.7b03817
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Photoluminescent isotypical phosphonate-based metal organic frameworks, [Ln(H(5)btp)]center dot 2H(2)O [where Ln(3+) = Tb3+ (1) or Gd3+ (2) and H(8)btp = [1,1'-biphenyl]-3,3',5,5'-tetrayltetrakis(phosphonic acid)] prepared under solvo(hydro)thermal conditions exhibit a three-dimensional supramolecular structure built up from phosphonate linkers bridging Li3+ ions. Single-crystal X-ray diffraction of 1 revealed hydrogen bonds along the a-axis between the crystallization water molecules and the phosphonate groups. The network features lozenge-shaped tubular channels with intermolecular interactions between adjacent organic ligand molecules. Crystal packing forces bring together two ligand biphenyl groups in a parallel arrangement, forming an excimer. A ratiometric luminescent thermometer operative close to room temperature was built based on the excimer and the D-5(4) -> F-7(5) Tb3+ emissions, exhibiting a maximum relative thermal sensitivity of 1.26%-K-1 and a minimum temperature uncertainty of 0.75 K at 319 K. This performance is similar to that of a thermometer based on the ligand singlet S-2,S-1 -> S-0 and metal D-5(4) -> F-7(5) transitions. Thus, the same MOF material provides two separate temperature data sets. This work shows the possibility of using excimer emissions in ratiometric luminescence thermometry.
引用
收藏
页码:9547 / 9554
页数:8
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