RT Journal Article
T1 Harnessing ligand design to develop primary and self-calibrated luminescent thermometers with field-induced single ion magnet behaviour in Dy3+ complexes
A1 Corredoira Vázquez, Julio
A1 González Barreira, Cristina
A1 García Deibe, Ana María
A1 Sanmartín Matalobos, Jesús
A1 Hernández Rodríguez, Miguel A.
A1 Brites, Carlos D. S.
A1 Carlos, Luis D
A1 Fondo Busto, María Matilde
K1 Luminescence properties
K1 Crystallographic analysis
K1 Macrocycle plane
K1 single-molecule magnet
AB Novel complexes {[Dy(LN6en)(OAc)2](NO3)}·2H2O (1·2H2O) and {[Dy(LN6prop)(OAc)2](NO3)}·CHCl3 (2·CHCl3), containing partially flexible symmetric N6 macrocycles, are reported. We explore the influence of the spacer length between two symmetrical N3 rigid moieties of the ligand on their structural, magnetic, and luminescence properties. Crystallographic analysis reveals the presence of Dy3+ ions in distorted tetradecahedral (1·2H2O) or bicapped square antiprism (2·CHCl3) environments. This underscores the increased flexibility of the LN6prop ligand, resulting in greater distortion of the N6 macrocycle plane. Both complexes exhibit single-molecule magnet behaviour under an optimal field of 2000 Oe, with 2·CHCl3 displaying the highest Ueff value of 127 K, despite its less planar N6 macrocycle. Luminescence measurements indicate that the ratio between the integrated intensity of the ligands and that of the the Dy3+ 4F9/2 → 6H13/2 transition can define secondary luminescent thermometers. Maximum relative thermal sensitivity values of 2.3 (1·2H2O) and 5.1% K−1 (2·CHCl3) are achieved. Furthermore, deconvolution of the 4F9/2 → 6H15/2 transition in 2·CHCl3 supports the previous determination of the energy barrier for magnetic relaxation. This permits the demonstration of the first example of a Dy3+ primary luminescent thermometer based on two thermally coupled Kramer's doublets of the 4F9/2 level. Remarkably, 2·CHCl3 is also the first self-calibrated luminescent thermometer with magnetic relaxation operating within the 86–211 K range, showcasing its potential in precise temperature sensing applications
PB Royal Society of Chemistry
PB Chinese Chemical Society
PB Peking University Press
YR 2024
FD 2024
LK http://hdl.handle.net/10347/32845
UL http://hdl.handle.net/10347/32845
LA eng
NO Corredoira Vázquez, J., González Barreira, C., García Deibe, Ana M., Sanmartín Matalobos, J., Hernández Rodríguez, M.A., Brites, Carlos D.S., Carlos, Luis D., Fondo, Matilde (2024). Harnessing ligand design to develop primary and self-calibrated luminescent thermometers with field-induced single ion magnet behaviour in Dy3+ complexes. "Inorganic chemistry frontiers", vol.11,1087-1098
NO This work was developed within the scope of the projectCICECO – Aveiro Institute of Materials, UIDB/50011/2020,UIDP/50011/2020, and LA/P/0006/2020, financed by nationalfunds through the FCT/MCTES (PIDDAC). This article is alsobased upon work from COST Action CA22131, supported byCOST (European Cooperation in Science and Technology). Theauthors acknowledge fruitful discussions with Dr AlbanN. Carneiro Neto (University of Aveiro) concerning ligand-tometal energy transfer. J. C. V. also thanks Xunta de Galicia forhis postdoctoral fellowship (ED481B-2022-068)
DS Minerva
RD 24 abr 2026