Molecular/Organic Ferromagnets

Abstract

Quantitative bulk ferromagnetic behavior has been established for the molecular/organic solid [Fe(III)(C(5)Me(5))(2)].(+)[TCNE].(-). Above 16 K the dominant magnetic interactions are along a 1-D chain and, near T(c), 3-D bulk effects as evidenced by the value of the critical exponents dominate the susceptibility. The extended McConnell model was developed and provides the synthetic chemist with guidance for making new molecular materials to study cooperative magnetic coupling in systems. Assuming the electron-transfer excitation arises from the POMO, ferromagnetic coupling by the McConnell mechanism requires stable radicals (neutral, cations/anions, or ions with small diamagnetic counterions) with a non-half-filled POMO. The lowest excited state formed via virtual charge transfer (retro or forward) must also have the same spin multiplicity and mix with the ground state. These requirements limit the structure of a radical to D(2d) or C>/=(3) symmetry where symmetry breaking distortions do not occur. Intrinsic doubly and triply degenerate orbitals are not necessary and accidental degeneracies suffice. To achieve bulk ferromagnetism, ferromagnetic coupling must be established throughout the solid and a microscopic model has been discussed. These requirements are met by [Fe(III)(C(5)Me(5))(2)].(+)[TCNE].(-). Additionally this model suggests that the Ni(III) and Cr(III) analogs should be antiferromagnetic and ferrimagnetic, respectively, as preliminary data suggest. Additional studies are necessary to test and further develop the consequences of these concepts. Some molecular/organic solids comprised of linear chains of alternating metallocenium donors (D) and cyanocarbon acceptors (A) with spin state S = 1/2 (...D.(+)A.(-)D.(+)A.(-)...) exhibit cooperative magnetic phenomena, that is, ferro-, antiferro-, ferri-, and metamagnetism. For [Fe(III)(C(5)Me(5))(2)].(+)[TCNE](-). (Me = methyl; TCNE = tetracyanoethylene), bulk ferromagnetic behavior is observed below the Curie temperature of 4.8 K. A model of configuration mixing of the lowest charge-transfer excited state with the ground state was developed to understand the magnetic coupling as a function of electron configuration and direction of charge transfer. This model predicts that ferromagnetic coupling requires stable radicals with a non-half-filled degenerate valence orbital and a charge-transfer excited state with the same spin multiplicity that mixes with the ground state. Ferromagnetic coupling must dominate in all directions to achieve a bulk ferromagnet. Thus, the primary, secondary, and tertiary structures are crucial considerations for the design of molecular/organic ferromagnets.