Formation of a Decanuclear Organometallic Dysprosium Complex via a Radical-Radical Cross-Coupling Reaction.

Over the years, polynuclear cyclic or torus complexes have attracted increasing interest due to their unique metal topologies and properties. However, the isolation of polynuclear cyclic organometallic complexes is extremely challenging due to their inherent reactivity, which stems from the labile and reactive metal-carbon bonds. In this study, the pyrazine ligand undergoes a radical-radical cross-coupling reaction leading to the formation of a decanuclear [(Cp*)20Dy10(L1)10]·12(C7H8) (1; where L1 = anion of 2-prop-2-enyl-2H-pyrazine) complex, where all DyIII metal centers are bridged by the anionic L1 ligand. Amongst the family of polynuclear Ln organometallic complexes bearing CpR2Lnx units, 1 features the highest nuclearity obtained to date. In-depth computational studies were conducted to elucidate the proposed reaction mechanism and formation of L1, while probing of the magnetic properties of 1, revealed slow magnetic relaxation upon application of a static dc field.

Probing the magnetic and magneto-optical properties of a radical-bridged Tb4 single-molecule magnet.

Reaction of the 1,2,4,5-tetrazine (tz˙-) radical and {Cp*2Tb}+ has yielded a tetranuclear radical-bridged TbIII single-molecule magnet. The strong Ln-radical coupling and the electronic differences of the TbIII ions in [(Cp*2Tb)4(tz˙-)4]·3C6H6 (1) are probed via magnetic, magneto-optical and computational studies.

Molecular Capacitors: Accessible 6- and 8-Electron Redox Chemistry from Dimeric "Ti(I)" and "Ti(0)" Synthons Supported by Imidazolin-2-Iminato Ligands.

Reduction of the diamagnetic Ti(III)/Ti(III) dimer [Cl2Ti(µ-NImDipp)]2 (1) (NImDipp = [1,3-bis(Dipp)imidazolin-2-iminato]-, Dipp = C6H3-2,6-iPr2) with 4 and 6 equiv of KC8 generates the intramolecularly arene-masked, dinuclear titanium compounds [(µ-N-η6-ImDipp)Ti]2 (2) and {[(Et2O)2K](µ-N-µ-η6:η6-ImDipp)Ti}2 (3), respectively, in modest yields. The compounds have been structurally characterized by X-ray crystallographic analysis, and inspection of the bond metrics within the η6-coordinated aryl substituent of the bridging imidazolin-2-iminato ligand shows perturbation of the aromatic system most consistent with two-electron reduction of the ring. As such, 2 and 3 can be assigned respectively as possessing metal centers in formal Ti(III)/Ti(III) and Ti(II)/Ti(II) oxidation states. Exploration of their redox chemistry reveal the ability to reduce several substrate equivalents. For instance, treatment of 2 with excess C8H8 (COT) forms the novel COT-bridged complex [(ImDippN)(η8-COT)Ti](µ-η2:η3-COT)[Ti(η4-COT)(NImDipp)] (4) that dissociates in THF solutions to give mononuclear (ImDippN)Ti(η8-COT)(THF) (5). Addition of COT to 3 yields heterometallic [(ImDippN)(η4-COT)Ti(µ-η4:η5-COT)K(THF)(µ-η6:η4-COT)Ti(NImDipp)(µ-η4:η4-COT)K(THF)2]n (6). Compounds 4 and 5 are the products of the 4-electron oxidation of 2, while 6 stands as the 8-electron oxidation product of 3. Reduction of organozides was also explored. Low temperature reaction of 2 with 4 equiv of AdN3 gives the terminal and bridged imido complex [(ImDippN)Ti(═NAd)](µ-NAd)2[Ti(NImDipp)(N3Ad)] (7) that undergoes intermolecular C-H activation of toluene at room temperature to afford the amido compound [(ImDippN)Ti(NHAd)](µ-NAd)2[Ti(C6H4Me)(NImDipp)] (8-tol). These complexes are the 6-electron oxidation products of the reaction of 2 with AdN3. Furthermore, treatment of 3 with 4 equiv of AdN3 produces the thermally stable Ti(III)/Ti(III) terminal and bridged imido [K(18-crown-6)(THF)2]{[(ImDippN)Ti(NAd)](µ-NAd)2K[Ti(NImDipp)]} (10). Altogether, these reactions firmly establish 2 and 3 as unprecedented Ti(I)/Ti(I) and Ti(0)/Ti(0) synthons with the clear capacity to effect multielectron reductions ranging from 4 to 8 electrons.

Radical-Bridged Ln4 Metallocene Complexes with Strong Magnetic Coupling and a Large Coercive Field.

Inducing magnetic coupling between 4f elements is an ongoing challenge. To overcome this formidable difficulty, we incorporate highly delocalized tetrazinyl radicals, which strongly couple with f-block metallocenes to form discrete tetranuclear complexes. Synthesis, structure, and magnetic properties of two tetranuclear [(Cp*2 Ln)4 (tz. )4 ]⋅3(C6 H6 ) (Cp*=pentamethylcyclopentadienyl; tz=1,2,4,5-tetrazine; Ln=Dy, Gd) complexes are reported. An in-depth examination of their magnetic properties through magnetic susceptibility measurements as well as computational studies support a highly sought-after radical-induced "giant-spin" model. Strong exchange interactions between the LnIII ions and tz. radicals lead to a strong magnet-like behaviour in this molecular magnet with a large coercive field of 30 kOe.

Probing optical and magnetic properties via subtle stereoelectronic effects in mononuclear DyIII-complexes.

Tapping into the secondary coordination environment of mononuclear DyIII-complexes leads to drastic changes in luminescence and magnetism. Visualization of effects induced by stereoelectronics on the opto-magnetic properties was achieved through subtle modifications in the ligand framework.

Enhancing Magnetic Communication between Metal Centres: The Role of s-Tetrazine Based Radicals as Ligands.

Although 1,2,4,5-tetrazines or s-tetrazines have been known in the literature for more than a century, their coordination chemistry has become increasingly popular in recent years due to their unique redox activity, multiple binding sites and their various applications. The electron-poor character of the ring and stabilization of the radical anion through all four nitrogen atoms in their metal complexes provide new aspects in molecular magnetism towards the synthesis of new high performing Single Molecule Magnets (SMMs). The scope of this review is to examine the role of s-tetrazine radical ligands in transition metal and lanthanide based SMMs and provide a critical overview of the progress thus far in this field. As well, general synthetic routes and new insights for the preparation of s-tetrazines are discussed, along with their redox activity and applications in various fields. Concluding remarks along with the limitations and perspectives of these ligands are discussed.