Machine Learning Prediction of the Experimental Transition Temperature of Fe(II) Spin-Crossover Complexes

Spin-crossover (SCO) complexes are materials that exhibit changes in the spin state in response to external stimuli, with potential applications in molecular electronics. It is challenging to know a priori how to design ligands to achieve the delicate balance of entropic and enthalpic contributions needed to tailor a transition temperature close to room temperature. We leverage the SCO complexes from the previously curated SCO-95 data set [Vennelakanti et al. J. Chem. Phys. 159, 024120 (<bold>2023</bold>)] to train three machine learning (ML) models for transition temperature (T-1/2) prediction using graph-based revised autocorrelations as features. We perform feature selection using random forest-ranked recursive feature addition (RF-RFA) to identify the features essential to model transferability. Of the ML models considered, the full feature set RF and recursive feature addition RF models perform best, achieving moderate correlation to experimental T-1/2 values. We then compare ML T-1/2 predictions to those from three previously identified best-performing density functional approximations (DFAs) which accurately predict SCO behavior across SCO-95, finding that the ML models predict T-1/2 more accurately than the best-performing DFAs. In addition, we study ML model predictions for a set of 18 SCO complexes for which only estimated T-1/2 values are available. Upon excluding outliers from this set, the RF-RFA RF model shows a strong correlation to estimated T-1/2 values with a Pearson's r of 0.82. In contrast, DFA-predicted T-1/2 values have large errors and show no correlation to estimated T-1/2 values over the same set of complexes. Overall, our study demonstrates slightly superior performance of ML models in comparison with some of the best-performing DFAs, and we expect ML models to improve further as larger data sets of SCO complexes are curated and become available for model training.