Here, we report the synthesis of two new sets of dibismuthbridged rare earth molecules. The first series contains a bridging diamagnetic Bi 2 2− anion, (Cp* 2 RE) 2 (μ-η 2 :η 2 -Bi 2 ), 1-RE (where Cp* = pentamethylcyclopentadienyl; RE = Gd (1-Gd), Tb (1-Tb), Dy (1-Dy), Y (1-Y)), while the second series comprises the first Bi 2 3− radical-containing complexes for any d- cryptand), which were obtained from one-electron reduction of 1-RE with KC 8 . The Bi 2 3− radical-bridged terbium and dysprosium congeners, 2-Tb and 2-Dy, are single-molecule magnets with magnetic hysteresis. We investigate the nature of the unprecedented lanthanide−bismuth and bismuth−bismuth bonding and their roles in magnetic communication between paramagnetic metal centers, through single-crystal X-ray diffraction, ultraviolet−visible/ near-infrared (UV−vis/NIR) spectroscopy, SQUID magnetometry, DFT and multiconfigurational ab initio calculations. We find a π z * ground SOMO for Bi 2 3− , which has isotropic spin−spin exchange coupling with neighboring metal ions of ca. −20 cm −1 ; however, the exchange coupling is strongly augmented by orbitally dependent terms in the anisotropic cases of 2-Tb and 2-Dy. As the first examples of p-block radicals beneath the second row bridging any metal ions, these studies have important ramifications for single-molecule magnetism, main group element, rare earth metal, and coordination chemistry at large.

The effects of external pressure on a high-performing dysprosocenium single-molecule magnet are investigated using a combination of X-ray diffraction, magnetometry and theoretical calculations. The effective energy barrier (Ueff) decreases from...

Modeling the structure of a {Mn19} cluster on an Au(111) surface reveals that exchange coupling constants vary grossly upon adsorption due to surface-induced structural distortions. This leads to significant variations in the ground state S values.

The recent discovery of metal–metal bonding and valence delocalization in the dilanthanide complexes (CpiPr5)2Ln2I3 (CpiPr5 = pentaisopropylcyclopentadienyl; Ln = Y, Gd, Tb, Dy) opened up the prospect of harnessing the 4f n 5dz2 1 electron configurations of non-traditional divalent lanthanide ions to access molecules with novel bonding motifs and magnetism. Here, we report the trinuclear mixed-valence clusters (CpiPr5)3Ln3H3I2 (1-Ln, Ln = Y, Gd), which were synthesized via potassium graphite reduction of the trivalent clusters (CpiPr5)3Ln3H3I3. Structural, computational, and spectroscopic analyses support valence delocalization in 1-Ln resulting from a three-center, one-electron σ bond formed from the 4dz2 and 5dz2 orbitals on Y and Gd, respectively. Dc magnetic susceptibility data obtained for 1-Gd reveal that valence delocalization engenders strong parallel alignment of the σ-bonding electron and the 4f electrons of each gadolinium center to afford a high-spin ground state of S = 11. Notably, this represents the first clear instance of metal–metal bonding in a molecular trilanthanide complex, and the large spin–spin exchange constant of J = 168(1) cm–1 determined for 1-Gd is only the second largest coupling constant characterized to date for a molecular lanthanide compound.

In this communication we have unveiled the importance of lanthanide dopant, to realize n-doping of GFETs with an exceptional ambient stability and enhanced mobility. An unconventional mechanism proposed for such phenomenon is well supported by various analytical methods and rationalized by computational calculations.