Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
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 Tc of 4.8 K for [FeIII(C5Me5)2]•+ [TCNE]•- (Me = methyl; TCNE = tetracyanoethylene). Replacement of FeIII with MnIII leads to a ferromagnet with a Tc of 8.8 K in agreement with mean-field models developed for this class of materials. Replacement with CrIII, however, leads to a ferromagnet with a Tc 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 Tc ≈ 400 K, which exceeds the thermal decomposition temperature of the material. This demonstrates that a magnetic material with a Tc 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.
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