The Investigation of Spin-Crossover Systems by Raman Spectroscopy: A Review

Abstract

Spin-crossover (SCO) is a well-documented phenomenon, being intensely investigated by a respectable number of researchers during the last decades. The conventional method for the investigation of SCO properties is by performing magnetic susceptibility measurements. On the other hand, Raman has also been proposed as a promising characterization method since it is a non-bulk technique and allows, along with the monitoring of the SCO behavior, the parallel deep characterization of structure and molecular structure modifications, while it can also facilitate the determination of the entropy change related to the SCO event. There are several review articles focused on the analysis of the SCO phenomenon, the emerging applications of SCO materials and the importance of SCO/polymer composites, and elaborating on the vibrational effects on the investigation of SCO complexes; however, there has been no attempt to review solely the existing research efforts of the investigation of SCO phenomenon based on Raman spectroscopy. The main scope of this review is to focus on the main features, the challenges, and the key role of Raman spectroscopy in the investigation of 3d mononuclear complexes (comprising mainly of iron(II) complexes) and Hofmann-type metal organic frameworks (MOFs) exhibiting the SCO behavior. In addition, special focus is devoted to the research studies in which in situ Raman measurements are performed for the investigation of SCO systems. Finally, novelties, current challenges, future perspectives, and the contribution of Raman spectroscopy toward the practical application of SCO complexes are discussed.

Keywords

• molecular inorganic chemistry
• spin-crossover
• Raman spectroscopy
• iron(II) complexes