Lanthanide Grafted Bipyridine Periodic Mesoporous Organosilicas (BPy-PMOs) for Physiological Range and Wide Temperature Range Luminescence Thermometry.

2,2'-bipyridine is the most widely used chelating ligand for developing metal complexes in coordination and supramolecular chemistry. Here, we present a series of three bipyridine periodic mesoporous organosilicas (BPy-PMOs) grafted with lanthanide -diketonate complex for the purpose of obtaining thermochromic materials, which can be employed as ratiometric temperature sensors. Such thermometers are based on the ratio of two emission intensity peaks and are not affected by factors such as alignment or opto-electronic drift of the excitation source and detectors. Three thermometric systems are studied: Dy-Dy, Tb-Sm and Tb-Eu with the first two showing very attractive performance. For the first two systems, some of the best reported to date relative sensitivities are observed. In the BPy-PMO@Dy(acac)3 system, it is very unusual that the 4I15/2 → 6H15/2 transition is already occupied at such low temperature as 200 K, which influences its thermometric behaviour. The Tb-Sm shows excellent performance in the physiological range, also when suspended in water. We have additionally confirmed that the BPy-PMO hybrid materials lack toxicity to human cells proving them very promising candidates for biomedical thermometric applications.