3 years ago

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

Excimer Formation in a Terbium Metal–Organic Framework Assists Luminescence Thermometry
Ana D. G. Firmino, Mariela Nolasco, Filipe A. Almeida Paz, Duarte Ananias, João Rocha, Luís D. Carlos, Ricardo F. Mendes
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 5D47F5 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 S2,1S0 and metal 5D47F5 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.

Publisher URL: http://dx.doi.org/10.1021/acs.chemmater.7b03817

DOI: 10.1021/acs.chemmater.7b03817

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