Spin Crossover in a Vacuum-Deposited Submonolayer of a Molecular Iron(II) Complex

J Phys Chem Lett. 2012 Dec 6;3(23):3431-4. doi: 10.1021/jz3011805. Epub 2012 Nov 9.

Abstract

Spin-state switching of transition-metal complexes (spin crossover) is sensitive to a variety of tiny perturbations. It is often found to be suppressed for molecules directly adsorbed on solid surfaces. We present X-ray absorption spectroscopy measurements of a submonolayer of [Fe(II)(NCS)2L] (L: 1-{6-[1,1-di(pyridin-2-yl)ethyl]-pyridin-2-yl}-N,N-dimethylmethanamine) deposited on a highly oriented pyrolytic graphite substrate in ultrahigh vacuum. These molecules undergo a thermally induced, fully reversible, gradual spin crossover with a transition temperature of T1/2 = 235(6) K and a transition width of ΔT80 = 115(8) K. Our results show that by using a carbon-based substrate the spin-crossover behavior can be preserved even for molecules that are in direct contact with a solid surface.

Keywords: N4 ligands; X-ray absorption spectroscopy; iron(II); magnetic molecules; monolayer; spin crossover; surfaces.