N‐rich porous polymer with isolated Tb3+‐ions displays unique temperature dependent behavior through the absence of thermal quenching

F. Vanden Bussche, A.M. Kaczmarek, S. K. P. Veerapandian, J. Everaert, M. Debruyne, S. Abednatanzi, R. Morent, N. De Geyter, V. Van Speybroeck, P. Van der Voort, C.V. Stevens
Chemistry - A European Journal
26 (67), 15596-15604


The challenge of measuring fast moving or small scale samples is based on the absence of contact betw een sample and sensor. Grafting lanthanides onto hybrid materials arises as one of the most promising accurate techniques to obtain noninvasive thermometers. In this w ork, a novel bipyridine based Porous Organic Polymer (bpyDATPOP) wasinvestigatedastemperaturesensorafter grafting w ith Eu(acac) 3 and Tb(acac) 3 complexes. The bpyDAT POP successfully showed temperature dependent behavior in the 10 ‐ 310 K range, proving the potential of amorphous, porous organic framew orks. More intriguingly, w e observed unique temperature dependent behavior; instead of the standard observed change in emission as a result of a change in temperature for both Eu 3+ and Tb 3+ , the emission spectrumof Tb 3+ remained constant. This w ork provides framework‐ and energy‐based explanations for the observed phenomenon. The conjugation in the bpyDAT POP framew ork is interrupted, creating energetically isolated Tb 3+ environments. Energy transferfromTb 3+ toEu 3+ isthereforeabsent,norenergybacktransfer from Tb 3+ to bpyDAT POP ligand (i.e. no thermal quenching) is detected.

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