Luminescence‐Driven Electronic Structure Determination in a Textbook Dimeric Dy^III‐Based Single‐Molecule Magnet

Abstract

A textbook dysprosium dinuclear complex based on acetylacetone ligands, [Dy2(acac)4(μ2‐acac)2(H2O)2], has been synthesized and fully characterized. This simple dimeric lanthanide complex shows well‐resolved solid‐state luminescence and behaves as a single‐molecule magnet under zero DC field. A seminal crystal‐field approach is used to marry both magnetism and luminescence in the frame of an energetic picture.

Luminescence, chiroptical, magnetic andab initiocrystal-field characterizations of an enantiopure helicoidal Yb(iii) complex

“…The proof of concept was then extended with the use of low -temperature luminescence measurements, allowing an improvement of the spectra's resolution by removing a sizable number of extra transitions corresponding to "hot bands". 12 However, the assignment of these hot bands is not straightforward and can be easily over-interpreted by the presence of additional effects such as vibronic ones. 11d Despite its wide use, ab-initio calculations might fail as well to provide accurate electronic structure information, particularly for strongly correlated systems such as ytterbium-based complexes, where electronic correlation and covalen t effects are important and remain challenging to tackle with ab-initio methods.…”

From Mono- to Polynuclear Coordination Complexes with a 2,2′-Bipyrimidine-4,4′-dicarboxylate Ligand

“…Typically, Lu–Lu distances in this structure are on the order of 6.7–6.9 Å. Although rare, , such an arrangement of molecule brings eight lanthanide (here Lu) centers into the proximity and is of significant interest in a wide range of applications such as luminescence − and in particular with properties related to Ln–Ln energy transfer processes, − ,− magnetism, , or quantum information processing. , …”

“…Typically, Lu−Lu distances in this structure are on the order of 6.7−6.9 Å. Although rare, 44,45 such an arrangement of molecule brings eight lanthanide (here Lu) centers into the proximity and is of significant interest in a wide range of applications such as luminescence 46−48 and in particular with properties related to Ln−Ln energy transfer processes, 49−51,16−18 magnetism, 52,53 or quantum information processing. 54,55 ■ CONCLUSION For the first time, the potential of the 2,2′-bipyrimidine-4,4′dicarboxylic acid (bpd 2− ) ligand as a building block for lanthanide coordination (Ln = Lu, Eu, or Tb) has been explored.…”

Chiral or Luminescent Lanthanide Single-Molecule Magnets Involving Bridging Redox Active Triad Ligand

“…Moreover, one could remark that the energy difference between two consecutive transitions is about 37(5) cm −1 leading to the suspicion that the four additional transitions may originate from the second crystal field sublevel of the excited 2 F 5/2 state as proposed on the right part of Figure 4 [65,66]. These so-called "hot bands" usually disappear upon the lowering of the temperature that depopulates upper excited states [28,[67][68][69]. Consequently, these "hot bands" as well as other contributions of weak intensities that appeared in the emission spectrum may be also attributed to the vibronic coupling between electronic transitions and low energy vibrational modes as recently suggested for such Yb III ion in molecular systems [38,70].…”

“…In a general manner, the addition of one or more physical properties to the SMM behavior paves the way to the design of multi-properties SMM as well as the study of a possible synergy between the different properties. Moreover, when chirality is added to the (luminescent) SMM behavior [21][22][23][24][25][26][27][28], chiral SMM [29], ferroelectric SMM [30] as well as chiral luminescent SMM [31][32][33][34][35][36] and magneto-chiral SMM [37,38] can be obtained. To these three properties, the introduction of redox-active ligands is of interest because it could permit to switch both optical and magnetic properties depending on the oxidation state of the ligand [39][40][41][42][43][44][45][46].…”