An imido ligand significantly enhances the effective energy barrier of dysprosium(iii) single-molecule magnets

Abstract

A very basic imido ligand that can strongly bind to the dysprosium(iii) ion and significantly enhance the effective energy barrier for magnetisation reversal is reported.

Single-Molecule Toroic Design through Magnetic Exchange Coupling

“…Ab initio calculations were performed on the experimental structures of 1Dy, 1Y, and 2Dy using the MOLCAS 8.0 computational package (see Supplemental Information for details). [50][51][52][53] For the sake of simplicity, we started from 2Dy, which comprises four non-equivalent Dy(III) centers ( Figure S15). The calculated g tensors for the lowest eight KDs are very anisotropic (g z z 20) with a pure jG15 =2D type (Table S12).…”

Differences in the Performance of Allyl Based Palladium Precatalysts for Suzuki‐Miyaura Reactions

“…[6e] Precatalysts supported by both monodentate phosphine and NHC ligands were evaluated as these ligands are the most commonly used in cross-coupling reactions and comparing results with ligands of both types would enable us to understand the generality of our conclusions. [3] The Suzuki-Miyaura reaction was used as the model reaction as it is by far the most prevalent cross-coupling reaction in synthetic chemistry. [14], [15] Reactions were performed using a range of substrates, including heteroaryl chlorides, sterically bulky aryl chlorides, and nontraditional electrophiles, such as aryl esters, all of which require slightly different conditions.…”

“…[2] These ligands also stabilize monoligated palladium(0), which is proposed to be the active species in many cross-coupling reactions, but they often have comparable expense to the palladium source. [3] Thus, the traditional route for forming the active species, the addition of excess ligand to a palladium(0) complex, is no longer attractive. Instead, several well-defined palladium(II) precatalysts with a 1:1 palladium to ligand ratio that are reduced in situ to palladium(0) have been developed and are now commercially available.…”

“…Instead, several well-defined palladium(II) precatalysts with a 1:1 palladium to ligand ratio that are reduced in situ to palladium(0) have been developed and are now commercially available. [3] Common examples of palladium(II) precatalysts include Buchwald palladacycles, [4] Organ's PEPPSI precatalysts, [5] Nolan's allyl-based systems, [2d,6] and the related 1-tertbutylindenyl-based precatalyst developed at Yale (Figure 1). [7] Although it would be valuable for researchers to understand the relative performance of the different types of precatalysts, comparing catalytic activity across different precatalyst classes is challenging because they are typically used under different reaction conditions and have different pathways for activation.…”

Assembling High-Temperature Single-Molecule Magnets with Low-Coordinate Bis(amido) Dysprosium Unit [DyN 2 ] + via Cl–K–Cl Linkage

“…46,47 Thus, linear one-/two-coordinate Dy III complexes were proposed. [48][49][50][51][52] However, the synthesis of the two-coordinate Dy III complex was quite challenging as the Dy 3+ ion had a large radius and favored a high coordination number. Inspiringly, low-coordinate Dy III complexes were thought to provide very strong axial anisotropy readily, which could lead to high-performance SMM behaviors.…”