Postsynthetic lanthanide functionalization of nanosized metal–organic frameworks for highly sensitive ratiometric luminescent thermometry

Abstract

A straightforward postsynthetic lanthanide functionalization strategy is developed for fabricating highly sensitive ratiometric luminescent nanothermometers based on nanosized MOFs, which highlights the ability of a broad range of nanosized MOFs to construct nanothermometers.

Lanthanide–Organic Framework Nanothermometers Prepared by Spray‐Drying

“…[ 1a ] Figure 5 a depicts the temperature dependence of the relative sensitivity of spraydrying prepared Tb 0.914 Eu 0.086 -PDA in the range 10-325 K. The maximum sensitivity value of 5.96 ± 0.04% K −1 attained at 25 K is, to the best of our knowledge, the highest one reported in the cryogenic range (<100 K) for luminescent thermometers, in particular when compared with the: i) Eu/Tb-based MOF nanothermometers of Cui et al, [ 20,21 ] Cadiau et al, [ 22 ] Rao et al, [ 33 ] Zhou et al, [ 34 ] Wei et al, [ 35 ] Shen et al, [ 36 ] and Zhao et al, [ 37 ] which, although using distinct host matrices, adopt the same defi nition for the thermometric parameter; and ii) the nanothermometers of D'Vries et al, [ 38 ] which take the ratio between I 1 (or I 2 ) and the broad triplet band intensity. Additionally, Figure 5 a shows that, using distinct host matrices, Eu/Tb-based MOF nanothermometers cover the 10-340 K range with relative sensitivities in excess of 0.5% K −1 .…”

“…a) Relative sensitivity of the spray-drying prepared Tb 0.914 Eu 0.086 -PDA thermometer (gray line) ranging from 6.0% K −1 (at 25 K) to 0.07% K −1 (at 325 K). The relative sensitivities of the MOF thermometers reported by Cadiau et al [ 22 ] (red), Cui et al [ 20,21 ] (orange and pink), Rao et al [ 33 ] (blue), D'Vries et al [ 38 ] (green), Zhou et al [ 34 ] (yellow), Wei et al [ 35 ] (black), Shen et al [ 36 ] (brown), and Zhao et al [ 37 ] (dark green) are also represented, for comparison. The solid lines are used for those thermometers whose thermometric parameter is defi ned as I 1 / I 2 , whereas the dashed lines are used for other thermometers whose thermometric parameter is defi ned as the integrated intensity ratio between I 1 (or I 2 ) and the broad triplet band intensity, [ 38 ] or as the ratio between I 2 and the emission luminescent perylene dye.…”

A portable luminescent thermometer based on green up-conversion emission of Er3+/Yb3+ co-doped tellurite glass

“…This parameter—which is expressed in units of percent change per degree Kelvin (% K −1 )—was defined in 2007 in the context of temperature optical sensors8, and it has been commonly used as a figure of merit to compare different thermometers, independently of their nature1414243. Many authors employ absolute maximum sensitivity for comparison among different host materials; however, S R has the advantage of being independent of the nature of the thermometer (i.e., mechanical, electrical, optical), thus allowing a quantitative comparison of different thermometry techniques.…”

Multi-Color Luminescence and Sensing of Rare Earth Hybrids by Ionic Exchange Modification

“…The luminescent properties of rare earth coordination compounds are very sensitive to their structural characteristics, coordination environment, and their interactions with guest species, which endows coordination compounds with inherent advantage in luminescent sensing [26][27][28][29]. Recently, these rare earth coordination compounds have unlimited potentials as chemical sensors, detecting cations, anions, small molecules, pH value and temperature [30][31][32][33][34][35][36][37][38][39].…”