Ferromagnetic nanoscale electron correlation promoted by organic spin-dependent delocalization.
We describe the electronic structure and the origin of ferromagnetic exchange coupling in two new metal complexes, NN-SQ-Co(III)(py)(2)Cat-NN (1) and NN-Ph-SQ-Co(III)(py)(2)Cat-Ph-NN (2) (NN = nitronylnitroxide radical, Ph = 1,4-phenylene, SQ = S = (1)/(2) semiquinone radical, Cat = S = 0 catecholate, and py = pyridine). Near-IR electronic absorption spectroscopy for 1 and 2 reveals a low-energy optical band that has been assigned as a Psi(u) --> Psi(g) transition involving bonding and antibonding linear combinations of delocalized dioxolene (SQ/Cat) valence frontier molecular orbitals. The ferromagnetic exchange interaction in 1 is so strong that only the high-spin quartet state (S(T) = (3)/(2)) is thermally populated at temperatures up to 300 K. The temperature-dependent magnetic susceptibility data for 2 reveals that an excited state spin doublet (S(T) = (1)/(2)) is populated at higher temperatures, indicating that the phenylene spacer modulates the magnitude of the magnetic exchange. The valence delocalization within the dioxolene dyad of 2 results in ferromagnetic alignment of two localized NN radicals separated by over 22 A. The ferromagnetic exchange in 1 and 2 results from a spin-dependent delocalization (double exchange type) process and the origin of this strong electron correlation has been understood in terms of a valence bond configuration interaction (VBCI) model. We show that ferromagnetic coupling promoted by organic mixed-valency provides keen insight into the ability of single molecules to communicate spin information over nanoscale distances. Furthermore, the strong interaction between the itinerant dioxolene electron and localized NN electron spins impacts our ability to understand the exchange interaction between delocalized electrons and pinned magnetic impurities in technologically important dilute magnetic semiconductor materials. The long correlation length (22 A) of the itinerant electron that mediates this coupling indicates that high-spin pi-delocalized organic molecules could find applications as nanoscale spin-polarized electron injectors and molecular wires.
Kirk
Martin L
ML
Department of Chemistry and Chemical Biology, The University of New Mexico, MSC03 2060, 1 University of New Mexico, Albuquerque, New Mexico 87131-0001, USA. mkirk@unm.edu
Shultz
David A
DA
Schmidt
Robert D
RD
Habel-Rodriguez
Diana
D
Lee
Hyoyoung
H
Lee
Junghyun
J
D004583:Electrons; D005290:Ferric Compounds / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry*; D008280:Magnetics; D009942:Organometallic Compounds / Q000737:chemistry*; D013696:Temperature
D005290:Ferric Compounds; D005609:Free Radicals; D009942:Organometallic Compounds; C001215:ferrite