Organic and Organometallic Molecular Magnetic Materials—Designer Magnets

Abstract Magnets composed of molecular species or polymers and prepared by relatively low‐temperature organic synthetic methodologies are a focus of contemporary materials science research. The anticipated properties of such molecular‐species‐based magnetic materials, particularly in combination with other properties associated with molecules and polymers, may enable their use in future generations of electronic, magnetic, and/or photonic/photronic devices ranging from information storage and magnetic imaging to static and low‐frequency magnetic shielding. A tutorial of typical magnetic behavior of molecular materials is presented. The three distinct models (intramolecular spin coupling through orthogonal orbitals in the same spatial region within a molecule/ion, intermolecular spin coupling through pairwise “configuration interaction” between spin‐containing moieties, and dipole—dipole, through‐space interactions) which enable the design of new molecular‐based magnetic materials are discussed. To achieve the required spin couplings for bulk ferro‐ or ferrimagnetic behavior it is crucial to prepare materials with the necessary primary, secondary, and tertiary structures akin to proteins. Selected results from the worldwide effort aimed at preparing molecular‐based magnetic materials by these mechanisms are described. Some organometallic solids comprised of linear chains of alternating metallocenium donors (D) and cyanocarbon acceptors (A) that is, …︁D •+ A •− D •+ A •− …︁, exhibit cooperative magnetic phenomena. Bulk ferromagnetic behavior was first observed below the critical (Curie) temperature T c of 4.8 K for Fe III (C 5 Me 5 ) 2 •+ TCNE •− (Me = methyl; TCNE = tetracyanoethylene). Replacement of Fe III with Mn III leads to a ferromagnet with a T c of 8.8 K in agreement with mean‐field models developed for this class of materials. Replacement with Cr III , however, leads to a ferromagnet with a T c lowered to 3.65 K which is at variance with this model. Extension to the reaction of a vanadium(o) complex with TCNE leads to the isolation of a magnet with a T c ≈ 400 K, which exceeds the thermal decomposition temperature of the material. This demonstrates that a magnetic material with a T c substantially above room temperature is achievable in a molecule/organic/polymeric material. Finally, a new class of one‐dimensional ferrimagnetic materials based on metalloporphins is discussed.