Holmium(iii) molecular nanomagnets for optical thermometry exploring the luminescence re-absorption effect

Abstract

Coordination complexes of lanthanide(3+) ions can combine Single-Molecule Magnetism (SMM) with thermally-modulated luminescence applicable in optical thermometry. We report an innovative approach towards high performance SMM-based optical thermometers which explores...

Reversible Humidity-Driven Transformation of a Bimetallic {EuCo} Molecular Material: Structural, Sorption, and Photoluminescence Studies

“…The energies of the part of cyanide stretching vibrations significantly exceeds the value of 2129 cm −1 found for the K 3 [Co(CN) 6 ] precursor confirming the presence of bridging cyanido mode ( Table S1 ) [ 57 ]. They are also very similar to those detected in other dinuclear lanthanide(III)–hexacyanidometallate(III) molecules ( Table S1 ) [ 45 , 57 ].…”

“…This means that the difference between the two indicated emission components of 1 and 2 is mainly related to the changes in the transition probability between the respective m J levels within the emissive and the ground multiplets. This can be assigned to the subtle modulation of the coordination geometry of Eu III complexes in 1 and 2 which can dramatically influence the detailed state composition of m J levels [ 45 ].…”

“…Such conjunction may not only enable the observation of lanthanide-centered UV–vis photoluminescence but can also result in the effective sensitization of the 4f-centered emission throughout the radiationless energy transfer process involving d-d/charge-transfer electronic states of cyanido-based molecular moieties [ 37 , 38 , 39 , 40 , 41 , 42 ]. In this context, in the last few years, we focused our attention on the design of novel emissive d-f cyanido-bridged coordination systems aiming at multifunctional luminescent molecule-based materials linking photoluminescent features with single-molecule magnetism, proton conductivity, and solvent sorption properties [ 43 , 44 , 45 ]. Thus, we contributed to the more general research idea of multimodal functionalization of luminescent lanthanide molecular systems including their exploration as magnetic luminescent thermometers [ 46 ], luminescent molecular ferroelectrics [ 47 ], or luminescent ionic conductors [ 48 ].…”

Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets

“…The conjunction of photoluminescence and molecular nanomagnetism is an efficient tool for better understanding of magnetic anisotropy by investigating the high-resolution emission spectra which represent the electronic structure of the ground manifold of lanthanide ions 24 , 25 . Moreover, the bifunctionality offered by luminescent SMMs has been recently recognized to be promising from the viewpoints of the switching of emission by a magnetic field 26 , as well as luminescent thermometry for electromagnetic SMM-based devices exhibiting the self-monitoring of temperature 27 – 29 .…”

Dinuclear Lanthanide(III) Complexes from the Use of Methyl 2-Pyridyl Ketoxime: Synthetic, Structural, and Physical Studies

“…In addition, we have been working with the analogues of mepaoH (R = H, Ph, Cl in Figure 1 ) to study the influence of R on the identity and properties of the products. Last, but not least, inspired by the recent advances in the field of opto-magnetic materials and especially in that of optical thermometers (Single-Molecule Magnets which display thermally controlled luminescence) [ 93 , 94 ], we are investigating the optical/magnetic properties of 4 – 6 and analogous dinuclear Ln(III) complexes with a variety of other neutral 2-pyridyl oximes as capping ligands. Some of the above-mentioned efforts are already well-advanced proving that we have only scratched the surface of the lanthanide(III)/2-pyridyl oxime chemistry, and our results will be reported soon.…”