Controlling the spin-crossover behavior of the [Cr(indenyl)] family ligand functionalization.

In this work, a computational method to study the spin-crossover (SCO) behavior of the [Cr(n-Meindenyl)2] family was carried out. Using the TPSSh/Def2TZVP method with the GD3BJ dispersion correction scheme, we computed the thermochemistry and transition temperatures (T1/2) for all members of this family, which are in excellent agreement with the available experimental data. Moreover, the computed data allow us to build a model that describes the effect of functionalizing the indenyl ligand in different positions on the spin-state energy gap and transition temperature. Our results show that the C4 and C7 positions of the indenyl ligand have a greater effect on tuning the SCO properties of such complexes. The model quantitatively reproduces the DFT calculations, thus providing a powerful tool to analyze and predict the SCO properties in any member of the [Cr(n-Meindenyl)2] family.