Chemical Design and Magnetic Ordering in Thin Layers of 2D Metal−Organic Frameworks (MOFs)

Through rational chemical design, and thanks to the hybrid nature of metal-organic frameworks (MOFs), it is possible to prepare molecule-based 2D magnetic materials stable at ambient conditions. Here, we illustrate the versatility of this approach by changing both the metallic nodes and the ligands in a family of layered MOFs that allows the tuning of their magnetic properties. Specifically, the reaction of benzimidazole-type ligands with different metal centers (MII = Fe, Co, Mn, Zn) in a solvent-free synthesis produces a family of crystalline materials, denoted as MUV-1(M), which order antiferromagnetically with critical temperatures that depend on M. Furthermore, the incorporation of additional substituents in the ligand results in a novel system, denoted as MUV-8, formed by covalently bound magnetic double layers interconnected by van der Waals interactions, a topology that is very rare in the field of 2D materials and unprecedented for 2D magnets. These layered materials are robust enough to be mechanically exfoliated down to a few layers with large lateral dimensions. Finally, the robustness and crystallinity of these layered MOFs allow the fabrication of nanomechanical resonators that can be used to detect─through laser interferometry─the magnetic order in thin layers of these 2D molecule-based antiferromagnets

Isoreticular two-dimensional magnetic coordination polymers prepared through pre-synthetic ligand functionalization

Chemical functionalization is a powerful approach to tailor the physical and chemical properties of two-dimensional materials, increase their processability and stability, tune their functionalities and, even, create new 2D materials. This is typically achieved through post-synthetic functionalization by anchoring molecules on the surface of an exfoliated 2D crystal, but it inevitably alters the long-range structural order of the material. Here we present a pre-synthetic approach that allows the isolation of crystalline, robust, and magnetic functionalized monolayers of coordination polymers. A series of five isoreticular layered magnetic coordination polymers based on Fe(II) centres and different benzimidazole derivatives (bearing a Cl, H, CH3, Br or NH2 side group) were first prepared. On mechanical exfoliation, 2D materials are obtained that retain their long-range structural order and exhibit good mechanical and magnetic properties. This combination, together with the possibility to functionalize their surface at will, makes them good candidates to explore magnetism in the 2D limit and to fabricate mechanical resonators for selective gas sensing

Stoichiometric and catalytic solid-gas reactivity of rhodium bis-phosphine complexes

The complexes [Rh­(ⁱBu₂PCH₂CH₂PⁱBu₂)­L₂]­[BAr^F₄] [L₂ = C₄H₆, (C₂H₄)₂, (CO)₂, (NH₃)₂; Ar^F = 3,5-C₆H₃(CF₃)₂] have been synthesized by solid−gas reactivity via ligand exchange reactions with, in some cases, crystallinity retained through single-crystal to single-crystal transformations. The solid-state structures of these complexes have been determined, but in only one case (L₂ = (NH₃)₂) is the cation ordered sufficiently to enable its structural metrics to be determined by single crystal X-ray diffraction. The onward solid-state reactivity of some of these complexes has been probed. The bis-ammonia complex [Rh­(ⁱBu₂PCH₂CH₂PⁱBu₂)­(NH₃)₂]­[BAr^F₄] undergoes H/D exchange at bound NH₃ when exposed to D₂. The bis-ethene complex [Rh­(ⁱBu₂PCH₂CH₂PⁱBu₂)­(C₂H₄)₂]­[BAr^F₄] undergoes a slow dehydrogenative coupling reaction to produce a material containing a 1:1 mixture of the butadiene complex and a postulated mono-ethene complex. The mechanisms of these processes have been probed by DFT calculations on the isolated Rh cations. All the solid materials were tested as heterogeneous catalysts for the hydrogenation of ethene. Complexes with weakly bound ligands (e.g., L₂ = (C₂H₄)₂) are more active catalysts than those with stronger bound ligands (e.g., L = (CO)₂). Surface-passivated crystals, formed through partial reaction with CO, allow for active sites to be probed, either on the surface or the interior of the single crystal