Slow Magnetic Relaxation in Unprecedented Mono-Dimensional Coordination Polymer of Ytterbium Involving Tetrathiafulvalene-Dicarboxylate Linker

Abstract

A one-dimensional compound has been constructed through a Yb III ion and bridging redox-active deprotonated 4,5-bis(carboxylic)-4 1 ,5 1 -methyldithiotetrathiafulvene. This polymer displays slow magnetic relaxation due to the planar magnetic anisotropy of the Yb III , which has been experimentally determined.

Asymmetric Ring Opening in a Tetrazine‐Based Ligand Affords a Tetranuclear Opto‐Magnetic Ytterbium Complex

“…Because dynamic electron correlation effects were taken properly into account in ab initio calculations, the discrepancies between experimental and calculated data can arise from the improper model system (omission of the fluorine substituents), plausible mixing of Yb 2+ /Yb 3+ states in the ground state wave function of 1 and/or a small diamagnetic impurity in the sample. Similar discrepancies between experimental and calculated χT and M data have also been reported for other Yb based single‐molecule magnets before and their origins have remained elusive [56, 91, 92] …”

“…The omission of fluorinated backbones of fod − ligands in the model system A might influence the calculated energy spectrum and magnetic properties of 1 because electronegative fluorine atoms in the proximity of coordinating atoms influence on the electron density distribution around metal centre that further has an small effect the energy spectra and magnetic properties of investigated systems as previously reported for dinuclear Dy‐ and Tb‐complexes with similar type fluorinated acac ligands [53, 54] . However, trimming down the size of 1 is required because the XMS‐CASPT2 calculations are not computationally feasible for 1 due to its large size but necessary to model the dynamic electron correlation effects outside of 4f orbital space that heavily influence on the splitting of the energy levels of ytterbium complexes [6, 53, 55–59] . Nonetheless, the validity of our model systems and chosen computational approach can be benchmarked against the experimental energy spectrum of 1 obtained from the emission measurements (Figure 5).…”

“…Similar discrepancies between experimental and calculated cT and Md ata have also been reported for other Yb based singlemolecule magnets before and their origins have remained elusive. [56,91,92] To evaluate the total magnetic interactions (J in which f ij is the angle between the main anisotropy axes of the interacting sites i and j. [93] The dipolar coupling constants were also calculated through non-collinear Ising model [Eq.…”

“…[53,54] However,t rimming down the size of 1 is required because the XMS-CASPT2 calculations are not computationally feasible for 1 due to its large size but necessary to model the dynamic electron correlation effects outsideo f 4f orbitals pace that heavily influence on the splitting of the energy levels of ytterbium complexes. [6,53,[55][56][57][58][59] Nonetheless,t he validity of our model systemsa nd chosen computational approach can be benchmarked against the experimental energy spectrum of 1 obtainedf rom the emission measurements ( Figure 5). Previous CASSCF calculations carried out for large magnetic metal clusters have also shown that any fragmentation of clusters might lead to the erroneous results when the calculated magnetic properties of clusters are investigated.…”

“…Among the lanthanide ions explored for the preparation of luminescent Ln-SMMs, [5][6][7][8] the late Kramers ion Yb 3 + hass hown great promise. Recently,t wo examples of luminescent Yb-SMMsw ith built-in thermometric capability were published.…”