Spin crossover (SCO) complexes exhibit changes in spin state in response to external stimuli and have applications in molecular electronics, making them challenging materials for computational design. We curate a data set of 95 Fe(II) SCO complexes (SCO-95) from the Cambridge Structural Database which have available low- and high-temperature crystal structures and, in most cases, confirmed experimental spin transition temperatures (T_1/2). We study these complexes using density functional theory (DFT) with thirty functionals spanning across multiple rungs of “Jacob’s ladder” to understand the effect of exchange-correlation functional on both electronic and Gibbs free energies. We also assess the effect of varying the Hartree-Fock exchange fraction (a_HF) in structures and properties from the B3LYP family of functionals. We identify three best-performing functionals, namely modified B3LYP (a_HF = 0.10), meta-generalized gradient approximation (GGA) M06-L, and meta-GGA hybrid TPSSh, accurately indicate SCO behavior for the majority of the complexes. Contrary to observations from prior studies, double-hybrids with higher a_HF values strongly stabilize high-spin states and exhibit poor performance in predicting SCO behavior. Computationally predicted T_1/2 values are consistent among the three functionals but show limited correlation to experimentally reported T_1/2 values or ranks. We rationalize these differences by the lack of crystal packing effects and counter-anions in the DFT calculations to aid prediction of experimentally observed phenomena like hysteresis and two-step SCO behavior. The SCO-95 set of 95 experimental SCO complexes thus presents opportunities for method development, both in terms of increasing model complexity and method fidelity.

Chenru Duan

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