Redox- and solvato-magnetic switching in a tetrathiafulvalene-based triad single-molecule magnet

Abstract

Simultaneous redox and solvato-magnetic switching was achieved for a dinuclear dysprosium single-molecule magnet involving an extended tetrathiafulvalene fused semiquinone based triad.

Redox Modulation of Field-Induced Tetrathiafulvalene-Based Single-Molecule Magnets of Dysprosium

“…In other words, the oxidation of the bridging triad led to an enhancement of the SMM performances. It is worth noting that a reverse trend was observed for the parent compounds based on the Dy(hfac) 3 units [36]. For the latter analogues, the strong degradation of the magnetic performances after oxidation of the bridging triad was imputed to both change of coordination number from 8 to 9 and the strong variation of intermolecular dipolar magnetic interaction because of the presence of hydrogen bond in the oxidized compound leading to a shortening of the intermolecular Dy-Dy distance from 9.962 Å to 6.071 Å.…”

“…On one hand, the 4,4′,7,7′-tetra-tert-butyl-2,2′-bi-1,3-benzodithiole-5,5′,6,6′-tetrone [32] and 2,2′-benzene-1,4-diylbis(6-hydroxy-4,7-di-tert-butyl-1,3benzodithiol-2-ylium-5-olate [33] ligands (H2SQ) (Scheme 1) were used to bridge magnetic lanthanide units [34,35]. On the other hand, the H2SQ ligand and its oxidized form 2,2′-cyclohexa-2,5-diene-1,4-diylidenebis(4,7-di-tert-butyl-1,3-benzodithiole-5,6-dione (Q) (Scheme 1) were associated with Ln(hfac)3 units (Ln = Dy III [36] and Yb III [37]) for modulating both magnetic and photophysical properties. In the present article, we propose to focus our attention on the H2SQ ligand and its oxidized form Q in the coordination reactions with the Dy(tta)3•2H2O units.…”

“…The replacement of the hfac − ancillary anions with tta − is known to change the magnetic performances of the target compound [29,[38][39][40]. Indeed, the resulting X-ray structures of the dinuclear complexes [Dy2(tta)6(H2SQ)] (Dy-H2SQ) and [Dy2(tta)6(Q)]•2CH2Cl2 (Dy-Q) highlighted new coordination spheres around the Dy III compared to those observed for their hfac − parents of formula [Dy2(hfac)6(H2SQ)]•CH2Cl2 and [Dy2(hfac)6(Q)]) [36] leading to the study of new magnetic properties. Then the modulation of the magnetic properties as consequence of the oxidation of the bridging triads was evaluated.…”

Rare‐Earth Metal Tetrathiafulvalene Carboxylate Frameworks as Redox‐Switchable Single‐Molecule Magnets

“…TTF and its derivatives have been widely studied as electron‐donor components for conductive, optoelectronic, and magnetic materials [6] . The electroactivity of the TTF moiety has been used as a switch to modulate the magnetic moment between metal nodes in molecular structure and extended solids [2g,h, 6g,h] . Utilizing MOFs, the function of TTF could be employed in porous solids [7] .…”

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

“…Moreover, functional molecular systems have been also recently recognized as promising materials extremely sensitive to many types of external stimuli. They include the presence of solvent vapors and variable external pressure which are the stimuli typically used for the tuning of physical properties of MOF materials and inorganic solids, respectively [ 20 , 21 ].…”