Tuning the Spin-Crossover Properties of the [(Cp1-R)2Mn] Metallocenes

In this work, we present a computational study using density functional theory (DFT) on how the single functionalization of the cyclopentadienyl ligand in
[(Cp^1-R)₂Mn] systems can be used to tune the spin-crossover properties in such systems. Using the OLYP functional, accurate values for the transition temperature (T_1/2) can be obtained, and our DFT methodology can be used to explore the effect that different substituents have on tuning such quantity. In particular, we show that the electronic structure of the [(Cp^1-R)₂Mn] can be tuned via the R group, allowing for a fine-tuning degree of the T_1/2 that expands between 0 and 400 K. Our results allow for a rational design of new manganocene based systems with tailored SCO properties.