Amélie Pialat

The development and integration of Single-Molecule Magnets (SMMs) into molecular electronic devices continue to be an exciting challenge. In such potential devices, heat generation due to the electric current is a critical issue that has to be considered upon device fabrication. To read out accurately the temperature at the submicrometer spatial range, new multifunctional SMMs need to be developed. Herein, we present the first self-calibrated molecular thermometer with SMM properties, which provides an elegant avenue to address these issues. The employment of 2,2′-bipyrimidine and 1,1,1-trifluoroacetylacetonate ligands results in a dinuclear compound, [Dy₂(bpm)(tfaa)₆], which exhibits slow relaxation of the magnetization along with remarkable photoluminescent properties. This combination allows the gaining of fundamental insight in the electronic properties of the compound and investigation of optomagnetic cross-effects (Zeeman effect). Importantly, spectral variations stemming from two distinct thermal-dependent mechanisms taking place at the molecular level are used to perform luminescence thermometry over the 5–398 K temperature range. Overall, these properties make the proposed system a unique molecular luminescent thermometer bearing SMM properties, which preserves its temperature self-monitoring capability even under applied magnetic fields.

Studies of three related Cd^IIsystems derived from the ligand 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine, reveal an exceptionally rare example of¹¹³Cd–¹¹³CdJcoupling that is detectable by solid-state NMR (²J_Cd–Cd= ∼65 Hz).

After more than 50 years, the synthesis and electronic structure of the first and only reported “U⁰ complex” [U(bipy)₄] (1) has been reinvestigated. Additionally, its one‐electron reduced product [Na(THF)₆][U(bipy)₄] (2) has been newly discovered. High resolution crystallographic analyses combined with magnetic and computational data show that 1 and its derivative 2 are best described as highly reduced species containing mid‐to‐high‐valent uranium ligated by redox non‐innocent ligands.

The imidation of acetanilides proceeds exclusively para‐selectively under iodine(III)‐mediated stoichiometric or catalyzed reaction conditions with good tolerance to various functional groups at both ortho or meta position.

The direct, nucleophilic imidation of acetanilide derivatives has been performed under mild, iodine(III)‐mediated or ‐catalyzed conditions, employing lithium triflimide as the nitrogen source. The reaction exhibits exclusive regioselectivity for the para position and shows a good tolerance for varied functional groups at both the ortho or meta positions. Preliminary mechanistic data suggest that the LiNTf₂ reagent plays a key role in the reactivity.

1D, 2D and 3D Ag^Icoordination polymers were isolated using nitrogen based 3,6-bis(2′-pyrimidyl)-1,2,4,5-tetrazine and 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine ligands.

An unprecedented trinuclear heteroleptic Ag^I complex was isolated using a stable multidentate 2,4,6‐tris(2‐pyrimidyl)‐1,3,5‐triazine (TPymT) ligand. The obtained compound is an efficient catalyst for the direct aziridination of terminal olefins.

Direct triflation of acetanilide derivatives with silver triflate has been accomplished under mild iodine(III)-mediated oxidative conditions. The reaction shows excellent regioselectivity for the para position and tolerates a range of ortho and meta substituents on the aromatic ring. This method is also compatible with the preparation of arylnonaflates in synthetically useful yields.