Molecule-based magnets are a broad, emerging class of magnetic materials that expand the materials properties typically associated with magnets to include low density, transparency, electrical insulation, and low-temperature fabrication, as well as combine magnetic ordering with other properties such as photoresponsiveness. Essentially all of the common magnetic phenomena associated with conventional transition-metal and rare-earth-based magnets can be found in molecule-based magnets. Although discovered less than two decades ago, magnets with ordering temperatures exceeding room temperature, very high (∼27.0 kOe or 2.16 MA/m) and very low (several Oe or less) coercivities, and substantial remanent and saturation magnetizations have been achieved. In addition, exotic phenomena including photoresponsiveness have been reported. The advent of molecule-based magnets offers new processing opportunities. For example, thin-film magnets can be prepared by means of low-temperature chemical vapor deposition and electrodeposition methods.

Molecule-based magnets display the full range of phenomena observed in conventional transition-metal and rareearth-based magnets, as well as unusual phenomena unique to themselves. These materials form in a wide range of one-, two-, and three-dimensional network structures, with disorder often playing a substantial role.

The notion of organic molecular materials showing metallic properties, such as electric conductivity or ferromagnetism, started several decades ago as a mere dream of some members of the chemical community. The goal was to create an assembly of organic molecules or macromolecules containing only light elements (C, H, N, O, S, etc.) and yet possessing the electron/hole mobility or spin alignment that is inherent in typical metals or their oxides and different from the isolated molecular materials. Organic molecular conductors initially were developed during the 1960s, but the first examples of organic molecular magnets took several more decades to be discovered, owing to the more subtle and complex structural and electronic aspects of these materials. The flurry of activity in this field can be traced to the widely held belief that even the most sophisticated properties can be rationally designed by a systematic modification of organic molecular structures. This motivation was further fueled by increased synthetic capabilities, especially for obtaining large organic molecules with suitable structures and topologies, and also by the spectacular progress of supramolecular chemistry for materials development witnessed in recent years. Also noteworthy is the pioneering work performed in the 1960s by several physical organic chemists who unraveled different ways of aligning spins within open-shell molecules (i.e., triplet diradicals, carbenes, etc.), working against nature's tendency to align them in an antiparallel manner. Magnetic interactions between unpaired electrons, located on the singly occupied molecular orbitals (SOMOs) of di- and polyradicals, or between the adjacent open-shell molecules in crystals, are a crucial issue in this evolving field. Thus, depending upon the symmetry, degeneracy,and topological characteristics of SOMOs and also on the mode of arrangement of the molecules in a crystal, the resulting interaction can align the neighboring spins parallel or antiparallel (see the introductory article by Miller and Epstein in this issue of MRS Bulletin).

The construction of more and more complex systems starting from elemental molecular units used as building blocks is propelling several disciplines of burgeoning interest, such as supramolecular chemistry, molecular electronics, and molecular magnetism. In the particular context of magnetic molecular materials, an attractive possibility for adding complexity to the material is to use a hybrid approach in which an organic component is combined with an inorganic one. Both purely organic and purely inorganic approaches (see the articles in this issue by Veciana and Iwamura and by Miller, respectively) have been used extensively to obtain molecule-based magnets. The combination of these two kinds of magnetic molecular components has also been successfully explored to design polymeric magnets of different dimensionalities (the metal-radical approach). In this last case, both components play a magnetic role. A step forward in achieving multifunctionality is to design hybrid molecular materials formed by two independent molecular networks, such as anion/cation salts or host/guest solids, whereby each network furnishes distinct physical properties to the solid. This novel class of materials is interesting because it can give rise to the development of materials in which two properties in the same crystal lattice coexist, or materials that exhibit improved properties over those of the individual networks, or to new, unexpected properties due to the mutual interactions between them. One can imagine, for example, the combination of an extended inorganic magnetic layer opening the pathway to cooperative magnetism, with an organic or organometallic molecule that acts as a structural component controlling the interlayer separation. If the molecule inserted between the layers has unpaired electrons, a hybrid compound is produced that combines cooperative magnetism and paramagnetism. Other suitable combinations, such as electronic conductivity and magnetism, or nonlinear optics and magnetism, can also be achieved by wisely choosing the constituent molecules. In this article, we report some relevant examples that illustrate the potential of this hybrid approach in the context of molecule-based magnetic materials.

Magnets based on metal oxides have been important for hundreds of years. Magnetite, Fe3O4, Co-doped γ-Fe2O3, and CrO2 are important examples. The oxide (O2-) bridge between the magnetic metal ions has filled p orbitals (Figure 1a) that provide the pathway for strong spin coupling. Albeit with twice as many atoms, cyanide (C≡N−) can bridge between two metal ions via its pair of empty antibonding orbitals (Figure 1b) and filled nonbonding orbitals. Even prior to a detailed understanding of either their composition or structure, magnetic ordering of several cyanide complexes, although at low temperature, was noted. The differing atoms at each end of the cyanide ion have different binding affinities to metal ions, and simple coordination compounds, for example, [FeII(CN)6]2− (ferrocyanide), with alkali cations can easily be made. Replacement of the alkali cations with transition-metal cations affords insoluble materials, for example FeIII4[FeII(CN)6]3 (Prussian blue). Prussian blue has been used as a pigment and as an electrochromic and electrocatalyst material. The structure of Prussian blue was elucidated to be cubic (isotropic) with ⟶FeII⟵C≡N⟶FeIII⟵N≡C⟶FeII⟵ linkages along all three crystallographic directions (Figure 2). The FeII … FeIII separation is ∼5 Å. However, based on the composition, this is an idealized structure, as one FeII site per unit cell is missing. Water fills the vacant sites as well as the channels present in the structure. Due to the structural defects, it has been a challenge to grow single crystals.

Magnets are widely used in a large number of applications, and their market is larger than that of semiconductors. Information storage is certainly one of the most important uses of magnets, and the lower limit to the size of the memory elements is provided by the superparamagnetic size, below which information cannot be permanently stored because the magnetization freely fluctuates. This occurs at room temperature for particles in the range of 10–100 nm, owing to the nature of the material. However, even smaller particles can in principle be used either by working at lower temperatures or by taking advantage of the onset of quantum size effects, which can make nanomagnets candidates for the construction of quantum computers.