Insights into D_4h@metal-symmetry single-molecule magnetism: the case of a dysprosium-bis(boryloxide) complex

Abstract

We report a D4h@Dy single-molecule magnet (SMM) with a Ueff energy barrier of 1565 K, one of the highest energy barriers for any 6-coordinate lanthanide SMM.

Emerging Trends on Designing High-Performance Dysprosium(III) Single-Molecule Magnets

“…There are also several mononuclear Dy­(III) SMMs designed by the predominant bond strategy with six coordinates reported in the last five years. For example, an imido ligand based [Dy­(Im Dipp N) 2 (Cl) 2 (THF) 3 ] (Im Dipp N = 2,6- i ProPhy) and boryloxide ligand based [Dy­(OB­(NArCH) 2 ) 2 (THF) 4 ]­[BPh 4 ] with U eff of 803 and 1565 K, respectively, are among the recent reports. Of the notable reports on HP-Dy–SMMs with six coordinate, Liddle and co-workers reported a bis­(methanediide) based Dy­(III) compound [Dy­(NCN) 2 ]­[K­(18C6)­(THF) 2 ] (NCN = {C­(PPh 2 NSiMe 3 ) 2 } 2– ) with T-shaped planar geometry (Figure a) .…”

“…Accordingly, monomeric Dy­(III) complexes realized by CF symmetry strategy having pentagonal bipyramidal ( D 5 h symmetry), − hexagonal bipyramidal ( D 6 h symmetry), − and square antiprismatic ( D 4 d symmetry) , geometric structures are among the remarkable examples reported in the last five years. As well, tetrahedral ( C 2 v symmetry), square pyramidal ( C 4 v symmetry), , trigonal bipyramidal ( D 3 h symmetry), and square bipyramidal ( D 4 h symmetry) − are notable works reported so far under the predominant bond strategy. Organometallic strategy producing Dy­(III) metallocene SMMs with the current T B record of 80 K using anionic aromatic ligands (e.g., cyclopentadienyl (Cp) derivatives) represents a promising route to design HP–SMMs .…”

Zero‐field Slow Magnetic Relaxation Behavior of Dy2 in a Series of Dinuclear {Ln2} (Ln=Dy, Tb, Gd and Er) Complexes: A Combined Experimental and Theoretical Study

“…Henceforth, research activity in the field of SMMs has been predominantly focused on quenching the QTM effect and increasing the T B to facilitate the incorporation of SMM in nanosized devices. The anisotropic energy barrier can be modulated by a subtle change of ligands fields, the coordination geometry around the metal center, based on steric effect and electronic effect, which provides relevant information regarding the design and assembly of advanced Ln III ‐based SMMs [7,8] . Utilizing these concepts, SMMs with U eff and T B values as high as 2220 K [8] and 80 K [9] respectively were reported.…”

Edaravone-Based Mononuclear Dysprosium(III) Single-Molecule Magnets

“…In general, high-performance Dy­(III)-SMMs could be realized by employing different strategies such as CF symmetry, predominant bond, organometallic, and strong magnetic coupling approaches . In particular, monomeric Dy­(III) complexes designed by the CF symmetry strategy such as pentagonal bipyramidal, − hexagonal bipyramidal, − and square antiprismatic, , as well as low coordinate complexes possessing predominant bonds, − are effective routes for pursuing high effective energy barrier ( U eff ) and large blocking temperature ( T B ). Furthermore, monomeric Dy­(III) metallocenes generated from anionic cyclopentadienyl (Cp) ligands , are also proved to be high-temperature SMMs with a current record T B of 80 K for the [(Cp i Pr5 )­Dy­(Cp*)]­[BPh 4 ] complex, where Cp i Pr5 = penta-isopropylcyclopentadienyl and Cp* = pentamethylcyclopentadienyl .…”