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. . 024120 ()] to train three machine learning (ML) models for transition temperature () 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 values. We then compare ML 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 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 values are available. Upon excluding outliers from this set, the RF-RFA RF model shows a strong correlation to estimated values with a Pearson's of 0.82. In contrast, DFA-predicted values have large errors and show no correlation to estimated 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.