Direct or sequential? Actually both! – Spin crossover in iron compounds

With the immense growth of the amount of information, the development of new principles in high-density data storage comes into the foreground. Exploiting spin magnetic moment for the storage of data is one of the perspective directions. Remarkably, the orientation of spin can be changed by absorption of light with high selectivity and this new magnetic state can live relatively long. Thus, studies of transition metal materials undergoing so-called spin crossover are growing in number. We have also put our two cents in the discussion closing down the debates whether the mechanism of spin transition is direct or sequential.

Usual tools to study spin flips comprise transient optical spectroscopic methods such as pump-probe spectroscopies. Our colleagues from Free University in Berlin have addressed spin crossover in classical material iron(II) tris-bipyridine with a new type of spectroscopy where photoionization is used as a probe and we have provided theoretical support for the interpretation of their entangled data. This study has been recently published on pages of ChemPhysChem journal:

A. Moguilevski, M. Wilke, G. Grell, S.I. Bokarev, S.G. Aziz, N. Engel, A.A. Raheem, O. Kühn, I.Yu. Kiyan, E.F. Aziz Ultrafast Spin Crossover in [FeII(bpy)3]2+: Revealing Two Competing Mechanisms by Extreme Ultraviolet Photoemission Spectroscopy ChemPhysChem 18 (2017) 465-469.


There has been formulated no unambiguous opinion in the community on the mechanism of light-driven spin flip in iron(II) tris-bipyridine. In this process, the singlet spin configuration (no unpaired electrons) is changing to the long-living quintet (four unpaired electrons with parallel spins) within sub-100 fs time upon excitation with 400-580 nm light. After a long discussion, it has been concluded that direct spin flip of two electrons is highly improbable and a manifold of triplet intermediate states needs to be involved in a sequential process. However, recently an indication of direct mechanism has been found.

In our study, we have observed both pathways and even determined the branching ratio between both direct and sequential channels. To our opinion, our study resolves the cognitive dissonance involving mutually exclusive assumptions and adds to the profound mechanistic understanding of the spin crossover.


Leave a Reply

Please log in using one of these methods to post your comment: Logo

You are commenting using your account. Log Out / Change )

Twitter picture

You are commenting using your Twitter account. Log Out / Change )

Facebook photo

You are commenting using your Facebook account. Log Out / Change )

Google+ photo

You are commenting using your Google+ account. Log Out / Change )

Connecting to %s