Materials based on metallic elements that have d orbitals and exhibit room temperature magnetism have been known for centuries and applied in a huge range of technologies. Development of room temperature carbon magnets containing exclusively sp orbitals is viewed as great challenge in chemistry, physics, spintronics and materials science. Here we describe a series of room temperature organic magnets prepared by a simple and controllable route based on the substitution of fluorine atoms in fluorographene with hydroxyl groups. Depending on the chemical composition (an F/OH ratio) and sp3 coverage, these new graphene derivatives show room temperature antiferromagnetic ordering, which has never been observed for any sp-based materials. Such 2D magnets undergo a transition to a ferromagnetic state at low temperatures, showing an extraordinarily high magnetic moment. The developed theoretical model addresses the origin of the room temperature magnetism in terms of sp2-conjugated diradical motifs embedded in an sp3 matrix and superexchange interactions via –OH functionalization.

Graphene, a single two-dimensional sheet of carbon atoms with an arrangement mimicking the honeycomb hexagonal architecture, has captured immense interest of the scientific community since its isolation in 2004. Besides its extraordinarily high electrical conductivity and surface area, graphene shows a long spin lifetime and limited hyperfine interactions, which favors its potential exploitation in spintronic and biomedical applications, provided it can be made magnetic. However, pristine graphene is diamagnetic in nature due to solely sp2 hybridization. Thus, various attempts have been proposed to imprint magnetic features into graphene. The present review focuses on a systematic classification and physicochemical description of approaches leading to equip graphene with magnetic properties. These include introduction of point and line defects into graphene lattices, spatial confinement and edge engineering, doping of graphene lattice with foreign atoms, and sp3 functionalization. Each magnetism-imprinting strategy is discussed in detail including identification of roles of various internal and external parameters in the induced magnetic regimes, with assessment of their robustness. Moreover, emergence of magnetism in graphene analogues and related 2D materials such as transition metal dichalcogenides, metal halides, metal dinitrides, MXenes, hexagonal boron nitride, and other organic compounds is also reviewed. Since the magnetic features of graphene can be readily masked by the presence of magnetic residues from synthesis itself or sample handling, the issue of magnetic impurities and correct data interpretations is also addressed. Finally, current problems and challenges in magnetism of graphene and related 2D materials and future potential applications are also highlighted.

The pentafluorophenyl esters of bis(pentafluorophenyl)borinic acid (C 6 F 5 ) 2 BOC 6 F 5 (2) and pentafluorophenylboronic acid C 6 F 5 B(OC 6 F 5 ) 2 (3) have been prepared and characterized by multinuclear NMR and X-ray analysis. VT NMR studies have shown that restricted rotation around the B-O bond in 2 occurs below 193 K, corresponding to ∆G q ) 35 kJ/mol for this process. This low barrier and the random torsion angles around the B-O bonds observed in the solid state structures of compounds 2, 3, and B(OC 6 F 5 ) 3 (4) suggest that these torsion angles are not related to pπ-pπ interactions between boron and oxygen, but more likely a consequence of the extensive intermolecular F-π interactions seen in the solid state structures. The Lewis acidity of 2, 3, and 4 has been compared with B(C 6 F 5 ) 3 (1), using various Lewis bases. All compounds 1-4 appear to be strong Lewis acids, whereby 4 interacts more strongly with hard bases whereas 1 binds more strongly to softer bases.

Understanding the links between nucleophilic/reductive strength of the environment, formation of radicals and point defect characteristics is crucial for achieving control over the functionalization of fluorographene.