Shining New Light on Multifunctional Lanthanide Single‐Molecule Magnets

Abstract

Single‐molecule magnets (SMMs) are at the forefront of new technological advances in quantum information processing and spintronics. Despite the recent impressive breakthroughs in extending the magnetic blocking temperatures beyond liquid‐nitrogen temperatures, significant challenges await in terms of integrating and addressing such compounds in devices. With this ultimate goal in mind, the design of multifunctional SMMs not only allows to imbue molecules of interest with specific properties that would allow for in situ monitoring of the SMM operation in real time, but can also provide critical insights into our understanding of the magnetic behaviour. In this Review, we highlight how magnetism and luminescence can be harmoniously combined within single molecules to achieve these objectives. The key design principles to attain the simultaneous combination of photoluminescence and slow relaxation of the magnetization are discussed, along with an outlook on how such molecules could be beneficial for emerging next‐generation spintronics devices.

Formation of Heteropolynuclear Lanthanide Complexes Using Macrocyclic Phosphonated Cyclam-Based Ligands

“…This syn structure is enforced by the requirement of the crossbridged azamacrocycle, which results in a closed configuration and contiguity of the two pyridyl functionalities. In the solid-state, this closed state is augmented by intramolecular π-π stacking between the two pyridyl groups (CntAr-CntAr = 3.6287(1) Å), and intramolecular hydrogen bonding between the nitrogen atoms of the bis-protonated cross-bridged cyclam cavity (N2-N3 = 2.7228 (1) Å; N4-N5 = 2.7550(1) Å) (See Supplementary Information, Section 3.2). It is important to note that in both cases the neutral zwitterionic forms have been crystallised in agreement with the potentiometric data determined for L1H4 and L2H4 (vide infra).…”

“…The title compound was synthesised according to the general procedure, except that the solution was acidified to pD = 5.4, to give [EuL1H] as a white solid (24 mg, 32.0 µmol, 44%). 1…”

“…Lanthanide coordination complexes are a privileged class of luminescent materials, exhibiting several distinctive optical characteristics including long-lived excited states, sharp emission bands which are generally unperturbed by the ligand field, 1 and the absence of a Stokes' shift. 2,3,4 These properties are a consequence of the valence electron configuration ([Xe]4f n , n = 0 -14), involving Laporte forbidden f-f transitions between heavily shielded f-orbitals.…”

A Theoretical Framework for Ratiometric Single Ion Luminescent Thermometers—Thermodynamic and Kinetic Guidelines for Optimized Performance

“…[ 159–166 ] More recent attempts reveal that lanthanides in mesoporous materials may be a promising addition to the field. [ 167–170 ] Usage of the lanthanides as luminescent ions even allows the combination of different functionalities such as luminescence thermometry and single‐ion magnetism [ 171,172 ] or solid‐state lighting. [ 173 ] Moreover, creative ways for novel alternative thermometry concepts using Boltzmann‐based thermometry in the ground states have also been presented, which have the potential to strongly enhance relative sensitivities.…”

Structural Characterization, Magnetic and Luminescent Properties of Praseodymium(III)-4,4,4-Trifluoro-1-(2-Naphthyl)Butane-1,3-Dionato(1-) Complexes

“…Moreover, complexes of Pr(III), Er(III) and Yb(III) containing the Schiff base N 2 ,N 3 -bis(anthracen-9ylmethylene)pyridine-2,3-diamine (SBL) showed in vitro cytotoxicity against some human cancer cell lines [26] and the role of Ln(III) complexes to bind, cleavage of DNA also in diagnosis, and monitoring the treatment of cancer disease was recently summarized [27]. In addition to these applications, the presence of large number of unpaired f-electrons and the large intrinsic magnetic anisotropy of the lanthanide compounds [3,[28][29][30][31][32] utilized a useful way in the design of molecular magnetic materials (SMMs) [3,[33][34][35][36][37][38][39][40][41][42][43].…”