Photomagnetic response in highly conductive iron(II) spin-crossover complexes with TCNQ radicals.

ABSTRACT

Co-crystallization of a cationic Fe(II) complex with a partially charged TCNQ(.δ-) (7,7',8,8'-tetracyanoquinodimethane) radical anion has afforded molecular materials that behave as narrow band-gap semiconductors, [Fe(tpma)(xbim)](X)(TCNQ)(1.5)⋅DMF (X=ClO4(-) or BF4(-); tpma=tris(2-pyridylmethyl)amine, xbim=1,1'-(α,α'-o-xylyl)-2,2'-bisimidazole). Remarkably, these complexes also exhibit temperature-and light-driven spin crossover at the Fe(II) center, and are thus the first structurally defined magnetically bistable semiconductors assembled with the TCNQ(.δ-) radical anion. Transport measurements reveal the conductivity of 0.2 S cm(-1) at 300 K, with the low activation energy of 0.11 eV.