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Excimer Formation in a Terbium Metal–Organic Framework Assists Luminescence Thermometry
Chemistry of Materials ( IF 7.2 ) Pub Date : 2017-10-31 00:00:00 , DOI: 10.1021/acs.chemmater.7b03817 Duarte Ananias 1 , Ana D. G. Firmino 1 , Ricardo F. Mendes 1 , Filipe A. Almeida Paz 1 , Mariela Nolasco 1 , Luís D. Carlos 1 , João Rocha 1
Chemistry of Materials ( IF 7.2 ) Pub Date : 2017-10-31 00:00:00 , DOI: 10.1021/acs.chemmater.7b03817 Duarte Ananias 1 , Ana D. G. Firmino 1 , Ricardo F. Mendes 1 , Filipe A. Almeida Paz 1 , Mariela Nolasco 1 , Luís D. Carlos 1 , João Rocha 1
Affiliation
Photoluminescent isotypical phosphonate-based metal–organic frameworks, [Ln(H5btp)]·2H2O [where Ln3+ = Tb3+ (1) or Gd3+ (2) and H8btp = [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 Ln3+ 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 5D4 → 7F5 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 S2,1 → S0 and metal 5D4 → 7F5 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.
中文翻译:
a金属-有机骨架中的准分子形成有助于发光测温。
基于光致发光的典型的基于膦酸酯的金属-有机骨架,[Ln(H 5 btp)]·2H 2 O [其中Ln 3+ = Tb 3+(1)或Gd 3+(2)和H 8 btp = [1,1在溶剂热(水)热条件下制备的'-联苯基] -3,3',5,5'-四基四(膦酸)]显示出由桥接Ln 3+离子的膦酸酯连接基构建的三维超分子结构。的单晶X射线衍射1揭示氢键沿着一个结晶水分子和膦酸酯基之间的长轴。该网络具有菱形管状通道,在相邻的有机配体分子之间具有分子间的相互作用。晶体堆积力将两个配体联苯基以平行排列的方式聚集在一起,形成一个准分子。根据准分子和5 D 4 → 7 F 5 Tb 3+排放量,建立了一个接近室温的比例发光温度计,其最大相对热敏度为1.26%·K –1,最小温度不确定度为0.75 K在319 K时的性能。该性能类似于基于配体单重态S 2,1的温度计的性能。→ S 0和金属5 D 4 → 7 F 5过渡。因此,相同的MOF材料提供两个单独的温度数据集。这项工作表明在比例发光发光测温法中使用准分子发射的可能性。
更新日期:2017-10-31
中文翻译:
a金属-有机骨架中的准分子形成有助于发光测温。
基于光致发光的典型的基于膦酸酯的金属-有机骨架,[Ln(H 5 btp)]·2H 2 O [其中Ln 3+ = Tb 3+(1)或Gd 3+(2)和H 8 btp = [1,1在溶剂热(水)热条件下制备的'-联苯基] -3,3',5,5'-四基四(膦酸)]显示出由桥接Ln 3+离子的膦酸酯连接基构建的三维超分子结构。的单晶X射线衍射1揭示氢键沿着一个结晶水分子和膦酸酯基之间的长轴。该网络具有菱形管状通道,在相邻的有机配体分子之间具有分子间的相互作用。晶体堆积力将两个配体联苯基以平行排列的方式聚集在一起,形成一个准分子。根据准分子和5 D 4 → 7 F 5 Tb 3+排放量,建立了一个接近室温的比例发光温度计,其最大相对热敏度为1.26%·K –1,最小温度不确定度为0.75 K在319 K时的性能。该性能类似于基于配体单重态S 2,1的温度计的性能。→ S 0和金属5 D 4 → 7 F 5过渡。因此,相同的MOF材料提供两个单独的温度数据集。这项工作表明在比例发光发光测温法中使用准分子发射的可能性。