Full-Range Ratiometric Detection of D₂O in H₂O by a Heterobimetallic Uranyl/Lanthanide Framework with 4f/5f Bimodal Emission

Abstract

A uranyl–europium heterobimetallic compound, (TEA)3[(UO2)6Eu­(H2O)4(PPA)6] (H3PPA = phosphonoacetic acid, TEA = tetraethylammonium cation), was synthesized under mild hydrothermal conditions. The emission spectrum contains characteristic electronic transition features of both Eu3+ and UO2 2+, while the peak intensity of Eu3+ is notably higher than that of UO2 2+. This is primarily attributed to the energy transfer from uranyl to europium in the structure. Significantly, a positive correlation between the Eu3+ peak intensity at 621 nm and the D2O content can be established in the aqueous system, while the uranyl peak intensity is almost unchanged, allowing for the full-range ratiometric detection of D2O in H2O.

A Highly Stable Yttrium Organic Framework as a Host for Optical Thermometry and D2O Detection

“…Given the labile nature of RE‐based coordination compounds, the OH/OD exchange process is fast (i.e., <2 min until unchanged intensity vs. time profiles), and the lifetime response of the (Y,Tb,Eu) 6 ‐MOF towards H 2 O or D 2 O exposure is shown to be reversible within ±2.5 % under alternated exposure to X =0.8 and X =0.2 conditions (Figure S22). Because of the limited number of D 2 O detection materials and the importance of this kind of sensing for chemical analysis and nuclear power production, [51] the results obtained herein confirm this additional potentiality of the (Y 0.89 Tb 0.10 Eu 0.01 ) 6 ‐MOF material.…”

“…Assuming a classical linear Stern‐Volmer relation (y 0 /y=1+K ap x, where K ap is an apparent Stern‐Volmer constant), a correlation coefficient of r 2 =0.9836 was obtained for the Eu 3+ decays, with a slope of 0.7573 with respect to the X fraction. This result denotes a lower sensitivity in comparison to recently reported luminescent D 2 O sensors, [51] but the general behaviour confirms the effectiveness of the MOF towards D 2 O detection in the full compositional range. Assuming an exponential Stern‐Volmer‐type relation (ln(y 0 /y)=K ap x, i.e., a positive deviation on y 0 /y due to large extent of quenching by OH oscillators), a higher correlation coefficient is obtained (r 2 =0.9857), with a slope of 0.5643.…”

“…H 2 O = 0.8 and X H 2 O = 0.2 conditions (Figure S22). Because of the limited number of D 2 O detection materials and the importance of this kind of sensing for chemical analysis and nuclear power production, [51] the results obtained herein confirm this additional potentiality of the (Y 0.89 Tb 0.10 Eu 0.01 ) 6 -MOF material.…”

Optimizing Photoluminescence Quantum Yields in Uranyl Dicarboxylate Complexes: Further Investigations of 2,5‐, 2,6‐ and 3,5‐Pyridinedicarboxylates and 2,3‐Pyrazinedicarboxylate

“…[(UO 2 ) 2 (3,5-pydc) 2 -(HCOO) 2 Ni(R,S-Me 6 cyclam)] (5) crystallizes as a heterometallic diperiodic network with the V 2 O 5 topology, and [PPh 4 ][UO 2 (OH)(2,3-pyzdc)] (6) is a diperiodic species with sql topology. All complexes have well-resolved uranyl emission spectra in the solid state, and three of them have photoluminescence quantum yields among the highest reported for uranyl carboxylate complexes, 44 % for 1, 71 % for 3, and 36 % for 6. radiation [5] or D 2 O, [6] or displaying aggregation-induced emission [7] can be singled out. The study of the emission properties of mixed uranyl-lanthanide systems is also an active field of research.…”

“…[ 1 ] A particular feature of uranyl emission spectra is the presence of a fine structure arising from vibrational coupling, which generally results in a well‐resolved pattern of at least four intense peaks. Associated with the richness of uranyl coordination chemistry, encompassing in particular a wide range of coordination polymers of varying periodicity, [ 2 ] as well as polynuclear closed species, [ 3 ] these luminescence properties have potential application in chemical sensors or other photoactive systems, [ 4 ] among which those able to detect ionizing radiation [ 5 ] or D 2 O, [ 6 ] or displaying aggregation‐induced emission [ 7 ] can be singled out. The study of the emission properties of mixed uranyl–lanthanide systems is also an active field of research.…”