Spin state of spin-crossover complexes: From single molecules to ultrathin films

The growth of spin-crossover Fe (1, 10-phenanthroline) ₂ (NCS) ₂ molecules on Cu (100) surfaces in the coverage range from 0. 1 to 1. 8 molecular layers was studied using a scanning tunneling microscope (STM) operated in ultrahigh vacuum at low temperature (4 K). STM imaging allowed us to extract the molecular adsorption geometry. While the first-layer molecules point their NCS groups toward the surface and their phenanthroline groups upwards, the adsorption geometry is reversed for the molecules in the second layer. For submonolayer coverages, a coexistence of molecules in the high- and low-spin states was found that is not correlated with the coverage. This coexistence is reduced for second-layer molecules, leading to a dominant spin state at low temperatures. Differential conductance spectra acquired at negative bias voltage on first- and second-layer molecules suggest that second-layer molecules are in the high-spin state and are partially electronically decoupled from the substrate. Furthermore, increasing the tip-to-sample voltage reduces the distance between the two lobes of the molecule. The current dependence of this effect suggests that a smooth spin crossover from a high- to a low-spin state occurs with increasing sample voltage. This analog spin-state switching is well described within a simple transition-state model involving modifications to the energy barriers between low- and high-spin states due to a tip-induced electric field through the Stark effect.