Spin crossover in Fe(phen)(2)(NCS)(2) complexes on metallic surfaces

• Published in: The Journal of chemical physics 2017-03, Vol.146 (9)
• Main Authors: Gruber, Manuel, Miyamachi, Toshio, Davesne, Vincent, Bowen, Martin, Boukari, Samy, Wulfhekel, Wulf, Alouani, Mebarek, Beaurepaire, Eric
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Other
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.4973511

In this review, we give an overview on the spin crossover of Fe(phen)(2)(NCS) (2) complexes adsorbed on Cu(100), Cu2N/Cu(100), Cu(111), Co/Cu(111), Co(100), Au(100), and Au(111) surfaces. Depending on the strength of the interaction of the molecules with the substrates, the spin crossover behavior can be drastically changed. Molecules in direct contact with non-magnetic metallic surfaces coexist in both the high-and low-spin states but cannot be switched between the two. Our analysis shows that this is due to a strong interaction with the substrate in the form of a chemisorption that dictates the spin state of the molecules through its adsorption geometry. Upon reducing the interaction to the surface either by adding a second molecular layer or inserting an insulating thin film of Cu2N, the spin crossover behavior is restored and molecules can be switched between the two states with the help of scanning tunneling microscopy. Especially on Cu2N, the two states of single molecules are stable at low temperature and thus allow the realization of a molecular memory. Similarly, the molecules decoupled from metallic substrates in the second or higher layers display thermally driven spin crossover as has been revealed by X-ray absorption spectroscopy. Finally, we discuss the situation when the complex is brought into contact with a ferromagnetic substrate. This leads to a strong exchange coupling between the Fe spin in the high-spin state and the magnetization of the substrate as deduced from spin-polarized scanning tunneling spectroscopy and ab initio calculation. Published