Using first principles calculations, we predict a complex multifunctional behavior in cobalt bis(dioxolene) valence tautomeric compounds. Molecular spin-state switching is shown to dramatically alter electronic properties and corresponding transport properties. This spin state dependence has been demonstrated for technologically relevant coordination polymers of valence tautomers as well as for novel conjugated polymers with valence tautomeric functionalization. As a result, these materials are proposed as promising candidates for spintronic devices that can couple magnetic bistability with novel electrical and spin conduction properties. Our findings pave the way to the fundamental understanding and future design of active multifunctional organic materials for spintronics applications.
■ INTRODUCTIONMolecular spintronics seeks to exploit the electronic structural diversity of molecules to harness the spin of the electron in novel and improved computing and information storage applications. 1−4 Significant material focus in this area has been placed on the class of conjugated organic semiconductors (e.g., rubrene and tris(hydroxyquinolato)-aluminum) that have found applications in organic optoelectronics devices. 5 These materials, while often diamagnetic, have been reported to show dramatic spin-dependent charge transport effects including giant magnetoresistance (GMR) 6,7 and tunneling magnetoresistance (TMR). 8−10 However, recent years have seen net advances in the use of novel molecular materials synthesized for specific spin properties. This includes design and applications of single molecular magnets, which can have large spin quantum numbers and can be integrated into thin films 11−13 suitable for device applications. 14,15 In addition, the conjugated ferrimagnetic coordination polymer V(TCNE)x 16 has very recently been employed as a thin film electrode in an all-organic TMR-based spin valve device. 17 A molecular design motif with significant promise for spintronics is the spin crossover phenomenon 18 in which a transition between high-spin and low-spin states of a coordination compound can be externally tuned by temperature, light, or applied pressure. This is very common in a number of Fe(II) compounds with nitrogen-containing ligands and has been suggested for many years as a route to molecular memory devices due to the prevalence of hysteretic effects in the spin transition. 19 Recently, both experiment 20 and theory 21,22 have suggested spin state dependence of electrical transport in Fe(II) spin crossover compounds making them prime candidates for molecular spintronics.A chemical elaboration of the spin crossover phenomenon can be established through the use of radical dioxolene ligands complexed to a cobalt coordination center in a class of compounds called valence tautomers (VTs). 23,24 In valence tautomers, a high-spin to low-spin transition on the Co is accompanied by an intramolecular electron transfer from the Co to a redox active ligand.This suggests a very dramatic coupling betwee...