Spin-Crossover Complexes

Kazuyuki Takahashi
2018 Inorganics  
Spin-crossover (SCO) is a spin-state switching phenomenon between a high-spin (HS) and low-spin (LS) electronic configurations in a transition metal center. The SCO phenomenon is widely recognized as an example of molecular bistability. The SCO compounds most widely studied are six-coordinate first-row transition metal complexes with d 4 -d 7 configurations. A relative small enthalpy variation between LS and HS states can be realized by coopetition between ligand field stabilization (LFS) and
more » ... ization (LFS) and spin pairing energies, which is illustrated by the Tanabe-Sugano diagrams in common coordination chemistry textbooks. Since an entropy variation in spin multiplicity from LS to HS is always positive, an increase in temperature can induce the transformation in Gibbs free energy from a positive to a negative sign, at which point SCO conversion occurs from the LS to HS state. Cambi and co-workers' pioneering work on the anomalous magnetic behaviors of mononuclear Fe(III) dithiocarbamate complexes [1] was first recognized as SCO phenomena in the early 1930s. However, progress on SCO complexes awaited the dissemination of ligand field theory into coordination chemistry. The concept of controlling LFS energies by substitution with different field strength ligands resulted in the corroboration of SCO phenomena in some Co(II) and Fe(II) complexes in the early 1960s. Moreover, subsequent findings that pressure [2] and light [3] can induce an SCO phenomenon may attract attention to SCO complexes. In the 1990s the demonstration of device applications using the SCO complex [4] illuminated the potential of SCO complexes in future practical applications in memory, display, and sensing devices. Figure 1 shows the number of published articles per year whose titles or topics contain the words "spin-crossover," "spin equilibrium," or their derivatives. Studies concerning SCO complexes have apparently increased since the 1980s; moreover, the number has more rapidly developed after the 2000s. The fundamentals and applications of SCO complexes have attracted growing interest not only in inorganic coordination chemistry but also in a wide range of relevant research fields.
doi:10.3390/inorganics6010032 fatcat:6g3duy4nurbo3jbhaecgvouxyq